Materials, methods of making, methods of use, and articles incorporating the materials

ABSTRACT

The present disclosure is directed to uncured compositions that comprise a mixture of an uncured rubber with a polymeric hydrogel which, when cured to form crosslinks in the rubber, form elastomeric materials. The present disclosure is also directed to methods of using the uncured compositions and the elastomeric materials. The elastomeric materials can be used to make and/or incorporated into various types of articles (e.g., footwear, apparel, sporting equipment, or components of each).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S.Non-Provisional application Ser. No. 16/165,476, having the title“MATERIALS, METHODS OF MAKING, METHODS OF USE, AND ARTICLESINCORPORATING THE MATERIALS”, filed on Oct. 19, 2018, which claims thebenefit of and priority to U.S. Provisional Application Ser. No.62/574,262, having the title “RUBBER COMPOSITIONS AND USES THEREOF”,filed on Oct. 19, 2017, and to U.S. Provisional Application Ser. No.62/693,740, having the title “COLOR CHANGE MATERIALS, METHODS OF MAKING,METHODS OF USE, AND ARTICLES INCORPORATING THE COLOR CHANGE MATERIALS”,filed on Jul. 3, 2018, and to U.S. Provisional Application Ser. No.62/703,513, having the title “MATERIALS, METHODS OF MAKING, METHODS OFUSE, AND ARTICLES INCORPORATING THE MATERIALS”, filed on Jul. 26, 2018,and to U.S. Provisional Application Ser. No. 62/743,380, having thetitle “COMPOSITE MATERIALS, METHODS OF MAKING, METHODS OF USE, ANDARTICLES INCORPORATING THE COMPOSITE MATERIALS”, filed on Oct. 9, 2018,the disclosures which are incorporated herein by reference in theirentireties.

BACKGROUND

Articles of apparel and sporting equipment of various types arefrequently used for a variety of activities including outdooractivities, military use, and/or competitive sports. The externallyfacing surfaces of the articles can be formed of elastomeric materials,including cured rubbers which include pigments or dyes. During the useof these articles, the externally facing surfaces of the articles mayfrequently make contact with water, either in the form of liquid water,water vapor, or wet ground.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a cross-sectional view of an article or a component of anarticle formed of an elastomeric material according to the teachings ofthe present disclosure.

FIG. 1B is a cross-sectional view of another article or component of anarticle formed of an elastomeric material according to the teachings ofthe present disclosure.

FIG. 1C is a cross-sectional view of a finished article that comprisesthe article or component of FIG. 1A.

FIG. 1D is a cross-sectional view of another finished article thatcomprises the article or component of FIG. 1B.

FIG. 2A is a perspective view of a finished article in the form of agarment comprising the article or component of FIG. 1A.

FIG. 2B is a perspective view of a finished article in the form of aball cap or helmet comprising the article or a component of FIG. 1B.

FIG. 2C is a perspective view of a finished article in the form of atire or wheel comprising the article or component of FIG. 1A.

FIG. 2D is a perspective view of a finished article in the form ofhiking equipment comprising the articles or components of FIGS. 1A and1B.

FIG. 2E is a perspective view of a finished article in the form of aprotective glove comprising the article or component of FIG. 1A.

FIG. 2F is a perspective view of a finished article in the form offootwear comprising the article or component of FIG. 1A.

FIG. 2G is a bottom-side view of the finished article of footwear ofFIG. 2F.

FIG. 3A is a side view of an example of footwear, while FIG. 3B is abottom view of an example of footwear.

FIGS. 4A and 4B illustrate cross-sections of an article of footwear.

FIG. 5A is a flowchart describing a method of forming the finishedarticle of footwear of FIGS. 2F and 2G.

FIG. 5B is a flowchart describing a method of preparing an uncuredcomposition or an elastomeric material.

FIG. 5C is a flowchart describing a method of forming an article or acomponent of an article comprising an uncured composition or anelastomeric material.

FIG. 5D is a flowchart describing a method of forming the finishedarticle of apparel or sporting equipment of FIGS. 2A-2E.

FIG. 6A is a perspective view of a test set-up used for mud pull-offtesting.

FIG. 6B is a diagram of the measured force applied during mud pull-offtesting plotted as a function of compressive displacement.

FIG. 7 is a diagram of the average mud pull-off force exhibited byarticles or components of articles that comprise the elastomericmaterial of the present disclosure.

FIG. 8A is a diagram of the engineering stress (MPa) applied to a “dry”article or component of an article plotted as a function of displacementdistance.

FIG. 8B is a diagram of the engineering stress (MPa) applied to a “wet”article or component of an article plotted as a function of displacementdistance.

FIG. 9A is a diagram and table highlighting the water uptake rate andoverall water uptake capacity of an article or component of an articlethat comprises various amounts of a hydrogel mixed with cured rubber.

FIG. 9B is a diagram and table highlighting the water uptake rate andoverall water uptake capacity of an article or a component of an articlethat comprises various amounts of another hydrogel mixed with the curedrubber of FIG. 9A.

FIG. 10 is a diagram of the water uptake rate measured for articles orcomponents of articles comprising various amounts of a hydrogel mixedwith different cured rubbers.

FIG. 11A is a photomicrograph of the mud on the surface of an article ora component of an article that comprises only a conventional curedrubber without a polymeric hydrogel distributed throughout the rubber.

FIG. 11B is a photomicrograph of the mud on the surface of an article ora component of an article that comprises an elastomeric materialincluding a cured rubber with a polymeric hydrogel distributedthroughout the rubber according to the teachings of the presentdisclosure.

FIG. 12 is a photomicrograph illustrating the swelling capacity of theelastomeric material formed according to the teachings of the presentdisclosure.

FIG. 13A is a photomicrograph of an elastomeric material including curedrubber with polyacrylic acid (PAA) distributed throughout the rubber,before and after exposure of the material to water in a Water CyclingTest.

FIG. 13B is a photomicrograph of an elastomeric material formedaccording to the teachings of the present disclosure in which apolymeric hydrogel is entrapped (e.g., physically entrapped) by a curedrubber, before and after exposure to water in a Water Cycling Test.

FIG. 14 is a chemical description of formulas F-1A to F-1E.

DESCRIPTION

The present disclosure, in general, provides for elastomeric materialswhich comprise a cured rubber and a polymeric hydrogel distributedthroughout the cured rubber, as well as methods of forming and using theelastomeric materials. It has been found that distributing the polymerichydrogel throughout an uncured rubber to form a composition which issubsequently cured, can result in an elastomeric material which, when itcontacts water, readily takes up water, reversibly, and undergoes achange in physical characteristics. In other words, the elastomericmaterial of the present disclosure combines the elastomeric propertiesof a cured rubber, which generally has a hydrophobic nature and alimited ability to take up water, with hydrophilic nature and ability totake up water, dry, and then again take up water, of a polymerichydrogel. The polymeric network formed in the elastomeric material bycuring the rubber with the polymeric hydrogel dispersed in it can alsoentrap at least a portion of the polymeric hydrogel present within thepolymeric matrix formed by the curing. In many examples of the resultingelastomeric material, a majority of or substantially all of thepolymeric hydrogel remains entrapped in the elastomeric material ratherthan migrating out of the elastomeric material when soaked in water orwhen repeatedly exposed to water. The water can be in the form of liquidwater (including aqueous solutions), water vapor, or wet ground (e.g.,wet soil, wet grass, wet pavement, etc.). As can be readily appreciated,an elastomeric material which retains both its durability, elastomericnature and ability to take up water on repeated exposure to water can beused in a variety of articles of manufacture, including articles whichcontact mud or soil during use, where the accumulation of mud or soil isnot desirable.

Due to the presence of uncured or partially cured rubber in the uncuredcomposition, curing the uncured composition in contact with anothermaterial (e.g., another uncured rubber, a crosslinkable polymer, or apolymer precursor) can result in chemical bonds (e.g., crosslinkingbonds, polymer bonds, etc.) forming between the elastomeric material ofthe present disclosure and the other material during curing. This makesit possible to bond other polymeric materials including conventionalrubber (i.e., rubber substantially free of the polymeric hydrogel)and/or different elastomeric materials of the present disclosure (e.g.,elastomeric materials having different formulations and/orcharacteristics) to one another during a curing process, without theneed to use adhesives.

The uncured compositions and/or elastomeric materials of the presentdisclosure can be used to make and/or be incorporated into various typesof articles (e.g., footwear, apparel, sporting equipment, and componentsof each, along with other consumer goods). The elastomeric material(e.g., dry or wet but not saturated), when contacted by water, can takeup water until it becomes saturated with water. As it takes up water,the elastomeric material undergoes a physical change that is reversible.The elastomeric material can cycle from dry to wet and will againundergo the same physical change. In other words, the physicaldimensions and/or physical properties of the elastomeric material changewith the level of water uptake or release. In some examples, when wet,the elastomeric material can be softer, less brittle, more compliant,and combinations thereof, as compared to the elastomeric material whendry. When wet, the elastomeric material can swell, increasing thelength, width and/or height of an element on an article. When wet, theelastomeric material can exhibit an increase in compressive compliance;and can, when compressed, expel water that was taken up previously; canhave a lubricious externally facing surface; and combinations thereof.The physical characteristics of the elastomeric materials when wet(e.g., compressive compliance, lubricity), as well as these physicalcharacteristic changes which can occur when the material is wet (e.g.,expelling water) can also serve to disrupt the adhesion of soil on thewet elastomeric material or at an interface including the wetelastomeric material, or disrupt the cohesion of particles to each otheron the wet elastomeric material, or both.

The elastomeric material described herein, as well as uncuredcompositions which, when cured, form the elastomeric material, can beused to make and/or be incorporated into various types of articles orcomponents of articles. The article can be an article of manufacturewhich comprises cured rubber such as tubing or a tire. The article canbe an article of footwear, a component of an article of footwear, anarticle of apparel, a component of an article of apparel, an article ofsporting equipment, or a component of an article of sporting equipment.In the example where the article is an article of footwear, theelastomeric material or a component including the elastomeric materialcan be incorporated into an upper of the footwear or into the sole ofthe footwear or both. The elastomeric material can be present on anexternally-facing area of the article. When the elastomeric material isincorporated into a sole for footwear, the elastomeric material can beground-facing in the footwear, such as on an outsole component of thesole.

The elastomeric material and/or uncured compositions described hereincan be incorporated into and used in finished articles or components offinished articles. The finished articles within the scope of the presentdisclosure generally include any article of manufacture including, butnot limited to, footwear, apparel, such as garments, and sportingequipment, such as balls, bats, clubs, protective gear, and hunting,hiking, or camping equipment, as well as consumer goods such as tubing,wheels, and tires, or the like, and are described in more detail herein.

The present disclosure is also directed to uncured compositions thatcomprise a mixture of an uncured rubber with a polymeric hydrogel which,when cured to form crosslinks in the rubber, form the elastomericmaterial. The present disclosure is also directed to methods of usingthe uncured compositions and the elastomeric materials.

The present disclosure provides for a composition comprising: a rubber;and a polymeric hydrogel; wherein, in the composition, the polymerichydrogel is distributed throughout the rubber. The rubber can be anuncured rubber or cured rubber. In some examples, at least a portion ofthe polymeric hydrogel in the elastomeric material is entrapped by thecured rubber. In the elastomeric material, the polymeric hydrogel can bephysically entrapped by the cured rubber. In the elastomeric material,the polymeric hydrogel can be chemically entrapped by the cured rubberthrough chemical bonds such as crosslinking bonds. In the elastomericmaterial, the polymeric hydrogel can be both physically entrapped by andchemically bonded to the cured rubber.

The present disclosure provides for an article comprising: anelastomeric material including a cured rubber and a polymeric hydrogel;wherein, in the elastomeric material, the polymeric hydrogel isdistributed throughout the cured rubber, and at least a portion of thepolymeric hydrogel present in the elastomeric material is entrapped bythe cured rubber.

The present disclosure provides for an article comprising a firstelastomeric material of the present disclosure. For example, a firstportion of the article can comprise the first elastomeric material. Thefirst portion can be externally-facing on the article. The firstelastomeric material can includes a mixture of a first cured rubber anda first polymeric hydrogel at a first concentration; wherein, in thefirst elastomeric material, the first polymeric hydrogel is distributedthroughout the first cured rubber and at least a portion of the firstpolymeric hydrogel present in the first elastomeric material isentrapped by the first cured rubber, wherein the first elastomericmaterial is capable of taking up water. In a particular example, thearticle is an article of footwear comprising: an upper; and a sole. Theupper can comprise the first elastomeric material. Alternatively oradditionally, the sole can comprise the first elastomeric material. Inthe example where the sole comprises the first elastomeric material, thefirst elastomeric material can be present in an outsole. The outsole canbe an outsole comprising a first region having a first elastomericmaterial; wherein the first region defines a portion of an externallyfacing side of the outsole.

The present disclosure also provides for when the article comprises asecond region including a second elastomeric material according to thepresent disclosure. The first region and the second region can beadjacent one another, wherein the second region defines a portion of theexternally facing side of the article, and wherein the secondelastomeric material includes a mixture of a second cured rubber and asecond polymeric hydrogel at a second concentration, wherein, in thesecond elastomeric material, the second polymeric hydrogel isdistributed throughout the second cured rubber and at least a portion ofthe second polymeric hydrogel present in the second elastomeric materialis entrapped by the second cured rubber.

The present disclosure also provides for an outsole including a firstelastomeric material; wherein the first elastomeric material forms afirst portion of an externally-facing side of the outsole; wherein thefirst elastomeric material includes a mixture of a first cured rubberand a first polymeric hydrogel at a first concentration, in which thefirst polymeric hydrogel is distributed throughout and entrapped by afirst polymeric network including the first cured rubber, and the firstelastomeric material has a water uptake capacity of at least 40 percentby weight based on a total weight of the first elastomeric materialpresent in the first portion.

The present disclosure also provides for a method of making an article,comprising: attaching a first component and a second component includingthe elastomeric material as described herein, to one another, therebyforming the article. The article can be any article of manufacture, forexample an article of footwear, an article of apparel, or an article ofsporting equipment. The present disclosure also provides for an articlecomprising a product of the method as described above or herein.

The present disclosure provides for a method of preparing a composition,the method comprising: mixing an uncured rubber and a polymeric hydrogeltogether to distribute the polymeric hydrogel throughout the uncuredrubber, forming the composition. The present disclosure also providesfor a composition prepared according to the method of above and asprovided herein. The present disclosure provides for an elastomericmaterial prepared according to the method above and described herein.

The present disclosure provides for a method of forming an elastomericmaterial, the method comprising: providing a composition including amixture of an uncured rubber and a polymeric hydrogel, wherein, in thecomposition, the polymeric hydrogel is distributed throughout theuncured rubber; and curing the composition to form the elastomericmaterial, wherein the polymeric hydrogel is distributed throughout thecured rubber and at least a portion of the polymeric hydrogel present inthe elastomeric material is entrapped by the cured rubber. The curingcan comprise forming chemical bonds between polymer chains of therubber, which forms a polymeric network of cured rubber chains thatphysically entraps at least a portion the polymeric hydrogel within theelastomeric material. The curing can comprise forming chemical bondswhich link polymer chains of the rubber to polymer chains of at least aportion of the polymeric hydrogel present in the elastomeric material,forming a polymeric network of the bonded cured rubber chains andhydrogel chains, which chemically entraps the at least a portion of thepolymeric hydrogel within the elastomeric material. The presentdisclosure provides for an elastomeric material prepared as describedabove and disclosed herein.

The present disclosure provides for a method of forming an article, themethod comprising: providing a composition including a mixture of anuncured rubber and a polymeric hydrogel; wherein, in the composition,the polymeric hydrogel is distributed throughout the uncured rubber;shaping the composition to form a shaped composition; and curing theshaped composition to cure the uncured rubber of the composition andform the article, the article comprising an elastomeric material inwhich the polymeric hydrogel is distributed throughout the cured rubberand at least a portion of the polymeric hydrogel in the elastomericmaterial is entrapped by cured rubber. The present disclosure alsoprovides for an article prepared according to the method above anddescribed herein.

The present disclosure also provides for a method of forming an articlecomprising a first component including a first material and a secondcomponent including an uncured composition or elastomeric material asdescribed herein. Attaching the first and second components can comprisecuring the first material in contact with the second material. Curingthe first material and the second material while in contact with eachother can form chemical bonds (e.g., crosslinking bonds or polymerbonds) between the first material and the second material, therebyattaching the first component to the second component using thesechemical bonds. In some cases, it may not be necessary to furtherreinforce the bond using an adhesive.

The present disclosure also provides for a method of forming an outsole,wherein the method comprises: shaping a first composition to form afirst portion of an externally-facing side an outsole, wherein the firstcomposition includes a mixture of a first uncured or partially curedrubber and a first polymeric hydrogel at a first concentration, whereinthe first polymeric hydrogel is distributed throughout the first uncuredor partially cured rubber; and curing the first portion to form a firstelastomeric material, thereby curing the first uncured or partiallycured rubber into a first fully cured rubber, and forming a firstpolymeric network including the first fully cured rubber in the firstelastomeric material, wherein the first polymeric hydrogel isdistributed throughout and entrapped by the first polymeric network.

This disclosure is not limited to particular aspects, embodiment orexamples described, and as such may, of course, vary. The terminologyused herein serves the purpose of describing particular aspects,embodiments and examples only, and is not intended to be limiting, sincethe scope of the present disclosure will be limited only by the appendedclaims.

Where a range of values is provided, each intervening value, to thetenth of the unit of the lower limit unless the context clearly dictatesotherwise, between the upper and lower limit of that range and any otherstated or intervening value in that stated range, is encompassed withinthe disclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges and are also encompassedwithin the disclosure, subject to any specifically excluded limit in thestated range. Where the stated range includes one or both of the limits,ranges excluding either or both of those included limits are alsoincluded in the disclosure.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual aspects, embodiments and examplesdescribed and illustrated herein has discrete components and featureswhich may be readily separated from or combined with the features of anyof the other several aspects, embodiments and examples without departingfrom the scope or spirit of the present disclosure. Any recited methodmay be carried out in the order of events recited or in any other orderthat is logically possible.

Aspects, embodiments and examples of the present disclosure will employ,unless otherwise indicated, techniques of material science, chemistry,textiles, polymer chemistry, textile chemistry, and the like, which arewithin the skill of the art. Such techniques are explained fully in theliterature.

Unless otherwise indicated, any of the functional groups or chemicalcompounds described herein can be substituted or unsubstituted. A“substituted” group or chemical compound, such as an alkyl, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester,ether, or carboxylic ester refers to an alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl, aryl, heteroaryl, alkoxyl, ester, ether, orcarboxylic ester group, has at least one hydrogen radical that issubstituted with a non-hydrogen radical (i.e., a substituent). Examplesof non-hydrogen radicals (or substituents) include, but are not limitedto, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, ether, aryl,heteroaryl, heterocycloalkyl, hydroxyl, oxy (or oxo), alkoxyl, ester,thioester, acyl, carboxyl, cyano, nitro, amino, amido, sulfur, and halo.When a substituted alkyl group includes more than one non-hydrogenradical, the substituents can be bound to the same carbon or two or moredifferent carbon atoms.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art of microbiology, molecular biology, medicinal chemistry, and/ororganic chemistry. Although methods and materials similar or equivalentto those described herein can be used in the practice or testing of thepresent disclosure, suitable methods and materials are described herein.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” may include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a support”includes a plurality of supports. In this specification and in theclaims that follow, reference will be made to a number of terms thatshall be defined to have the following meanings unless a contraryintention is apparent.

As used herein, the term “weight” refers to a mass value, such as havingthe units of grams, kilograms, and the like. Further, the recitations ofnumerical ranges by endpoints include the endpoints and all numberswithin that numerical range. For example, a concentration ranging from40 percent by weight to 60 percent by weight includes concentrations of40 percent by weight, 60 percent by weight, and all water uptakecapacities between 40 percent by weight and 60 percent by weight (e.g.,40.1 percent, 41 percent, 45 percent, 50 percent, 52.5 percent, 55percent, 59 percent, etc.). This will also apply to parts per hundredresin (phr).

As used herein, the term “providing”, such as for “providing astructure”, when recited in the claims, is not intended to require anyparticular delivery or receipt of the provided item. Rather, the term“providing” is merely used to recite items that will be referred to insubsequent elements of the claim(s), for purposes of clarity and ease ofreadability.

As used herein, the phrase “consist essentially of” or “consistingessentially of” refer to the feature being disclosed as having primarilythe listed feature without other active components (relative to thelisted feature) and/or those that do not materially affect thecharacteristic(s) of the listed feature. For example, the elastomericmaterial can consist essentially of a polymeric hydrogel, which meansthat second composition can include fillers, colorants, etc. that do notsubstantially interact with or interact with the change the function orchemical characteristics of the polymeric hydrogel. In another example,the polymeric hydrogel can consist essentially of a polycarbonatehydrogel, which means that the polymeric hydrogel does not include asubstantial amount or any amount of another type of polymer hydrogelsuch as a polyetheramide hydrogel or the like.

As used herein, the terms “at least one” and “one or more of” an elementare used interchangeably, and have the same meaning that includes asingle element and a plurality of the elements, and may also berepresented by the suffix “(5)” at the end of the element. For example,“at least one polyurethane”, “one or more polyurethanes”, and“polyurethane(s)” may be used interchangeably and have the same meaning.

Aspects of the present disclosure provide for a composition and anelastomeric material. The composition includes an uncured rubber and apolymeric hydrogen, wherein the polymeric hydrogel is distributedthroughout the uncured rubber. In the elastomeric material, the rubberis cured so that at least a portion of the polymeric hydrogel dispersedthroughout the cured rubber is entrapped by the cured rubber. Ingeneral, the uncured rubber alone, or the uncured rubber and thepolymeric hydrogel in the composition can undergo a reaction (e.g.,crosslinking reaction) to form the elastomeric material.

In regard to the composition, the composition includes the uncuredrubber and the polymeric hydrogel, where the polymeric hydrogel isdistributed throughout the uncured rubber. Also, the composition caninclude additional ingredients such as crosslinking agents, colorants,fillers, and the like. Additional details regarding the uncured rubberand polymeric hydrogel are provided below and herein.

When these compositions are cured to crosslink at least the uncuredrubber, the elastomeric material which is formed by the curing iscapable of taking up water and, when wet, including when saturated,provides a lubricious surface while maintaining sufficient abrasionresistance for use on externally-facing surfaces, such asexternally-facing surfaces of any article of manufacturing, includinggarments, articles of footwear, and articles of sporting equipment. Thehigh level of entrapment of the polymeric hydrogel by the cured rubberin the elastomeric material is indicated by the stability of theelastomeric material when soaked in water. For example, the WaterCycling Test using the Sampling Procedures described below, can be usedto test the stability of the elastomeric materials. In particularexamples, weight losses of less than about 15 weight percent (due tomigration of polymeric hydrogel out of the elastomeric material) areobserved.

The crosslinking agent can be a crosslinking agent for crosslinkinguncured or partially cured rubber. The crosslinking agent can include acrosslinking agent activated by actinic radiation. For example, thecrosslinking agent can be a thermally initiated crosslinking agent, or acrosslinking agent initiated by ultra-violet (UV) radiation. Thethermally initiated crosslinking agent may be, without limitation, asulfur-based crosslinking agent or a peroxide-based crosslinking agent.The uncured rubber may be an UV radiation curable rubber, and thecrosslinking agent can be an initiator for crosslinking the radiationcurable rubber upon exposure to UV radiation.

The present disclosure also provides for the elastomeric material thatincludes the cured rubber and the polymeric hydrogel where the polymerichydrogel is distributed throughout the cured rubber and at least aportion (e.g., about 1 percent to 100 percent) of the polymeric hydrogelin the elastomeric material is physically entrapped by the cured rubberand a portion can optionally (e.g., about 0 to 50 percent) be chemicallybonded or crosslinked with the cured rubber. In addition, theelastomeric material can be chemically bonded or crosslinked with curedrubber in an adjacent layer (e.g., traction element such as lugs orcleats, an upper, or other element in an article).

In addition, the composition (e.g., including the uncured rubber and thepolymeric hydrogel) and elastomeric material can optionally include oneor more colorants such as dyes and pigments, which can be homogeneouslyor heterogeneously distributed within the composition and elastomericmaterial. The selection of one or more colorants and the distribution ofthe colorants can be random or selected to achieve a desired aestheticeffect.

Referring to FIGS. 1A-1D, the article or component 15 of a finishedarticle 1 comprises a first surface 10 configured to beexternally-facing when the article or component is present in a finishedarticle 1; and a second surface 20 that opposes the first surface 10.The second surface 20 is located such that it can be optionally attached(e.g., affixed, adhered, coupled, bonded, etc.) with a substrate 25,which makes up part of the finished article 1. When desirable, thefinished article 1 may be an article of apparel or sporting equipment.In the case of an article of footwear, the article or component may bean outsole and the substrate may be a midsole or an upper. The component15 comprises an elastomeric material 16, such that at least a portion ofthe first surface 10 comprises a mixture of a polymeric hydrogel and acured rubber. This elastomeric material may represent the reactionproduct of a composition that comprises a mixture of an uncured rubberand the hydrogel. In other words, the elastomeric material 16 is presentat or forms the whole of or part of an outer surface of the article orcomponent 15. When the article or component 15 is included in an articleof apparel or sporting equipment 1, the elastomeric material 16 definesat least a portion of an exterior surface of the article 1 on a side,the bottom or the top of the article 1.

According to the present disclosure, the article or component 15 canextend across an entire externally-facing surface (shown in FIGS. 1A and10), such as an entire bottom surface of an article. However, in analternative aspect of the present disclosure, the crosslinkedelastomeric material 16 can be present as one or more segments of thearticle or component 15 that are present at separate, discrete locationson an externally-facing side or surface of a finished article 1. Forinstance, as shown in FIG. 1B, the material can alternatively be presentas discrete segments 16 secured to the surface of a substrate 25 that ispart of the finished article 1. In this example, the remaining region 17of the externally-facing surface, such as the remaining bottom surfaceof an outsole, can be free of the elastomeric material and comprise onlythe cured rubber or another material formulation.

The article can include the elastomeric material as described herein. Ina particular example, the article is an article of footwear thatincludes an upper and an outsole comprising a first region having afirst elastomeric material. The first region defines a portion of anexternally facing side or surface of the outsole, so that upon uptake ofwater, the elastomeric material undergoes a physical change. The articleof footwear can include more than one type of elastomeric material inthe same or different regions and/or other types of materials in thesame or different regions.

Various ways in which the elastomeric material have been presentedherein, but the elastomeric material may be used in other ways orvarious combinations to achieve appealing aesthetic change to thearticle.

The elastomeric material can be incorporated into various forms such asmolded components, textiles, films and the like. For example, the moldedcomponent, textile or film can be used in apparel (e.g., shirts,jerseys, pants, shorts, gloves, glasses, socks, hats, caps, jackets,undergarments) or components thereof, containers (e.g., backpacks,bags), and upholstery for furniture (e.g., chairs, couches, car seats),bed coverings (e.g., sheets, blankets), table coverings, towels, flags,tents, sails, tubing, wheels, tires, and parachutes. In addition, theelastomeric material can be used to produce components or other itemssuch as molded components, textiles, films and the like that aredisposed on the article, where the article can be striking devices(e.g., bats, rackets, sticks, mallets, golf clubs, paddles, etc.),athletic equipment (e.g., golf bags, baseball and football gloves,soccer ball restriction structures), protective equipment (e.g., pads,helmets, guards, visors, masks, goggles, etc.), locomotive equipment(e.g., bicycles, motorcycles, skateboards, cars, trucks, boats,surfboards, skis, snowboards, etc.), balls or pucks for use in varioussports, fishing or hunting equipment, furniture, electronic equipment,construction materials, eyewear, timepieces, jewelry, and the like.

In the example where the article of the present disclosure is an articleof footwear, it may be designed for a variety of uses, such as sporting,athletic, military, work-related, recreational, or casual use.Primarily, the article of footwear is intended for outdoor use onunpaved surfaces (in part or in whole), such as on a ground surfaceincluding one or more of grass, turf, gravel, sand, dirt, clay, mud, andthe like, whether as an athletic performance surface or as a generaloutdoor surface. However, the article of footwear may also be desirablefor indoor applications, such as indoor sports including dirt playingsurfaces for example (e.g., indoor baseball fields with dirt infields).

The article of footwear can be designed use in outdoor sportingactivities, such as global football/soccer, golf, American football,rugby, baseball, running, track and field, cycling (e.g., road cyclingand mountain biking), and the like. The article of footwear canoptionally include traction elements (e.g., lugs, cleats, studs, andspikes as well as tread patterns) to provide traction on soft andslippery surfaces, wherein the elastomeric material can be locatedbetween or among the traction elements and optionally on the sides ofthe traction elements, but not on the surface of the traction elementthat directly contact the ground or surface during wear. In other words,the terminal ends of the traction elements can be substantially free ofthe elastomeric material of the present disclosure. Cleats, studs andspikes are commonly included in footwear designed for use in sports suchas global football/soccer, golf, American football, rugby, baseball, andthe like, which are frequently played on unpaved surfaces. Lugs and/orexaggerated tread patterns are commonly included in footwear includingboots design for use under rugged outdoor conditions, such as trailrunning, hiking, and military use.

The elastomeric material of the present disclosure can be incorporatedinto articles such as footwear or components thereof, apparel orcomponents thereof, sporting equipment or components thereof. Theelastomeric material can be formed into a structure (e.g., outsole) thatcan have a range of dimensions depending upon the use. In one aspect,the elastomeric material can be used in an outsole or as a layer in anoutsole and can a thickness of about 0.1 millimeters to 10 millimeters,about 0.1 millimeters to 5 millimeters, about 0.1 millimeters to 2millimeters, about 0.25 millimeters to 2 millimeters, or about 0.5millimeters to 1 millimeter, where the width and length can varydepending upon the particular application (e.g., article to beincorporated into).

Referring once again to FIGS. 1C and 1D, at least a portion of thesecond surface of the component 15 is attached to a substrate 25 thatcomprises, without limitation, a polymeric foam, a polymeric sheet, atextile including a natural or synthetic leather, a molded solidpolymeric material, or a combination thereof. The substrate 25 cancomprise a thermoset polymeric material, a thermoplastic polymericmaterial, or a combination thereof. The thermoplastic polymeric materialmay include, without limitation, a thermoplastic polyurethane, athermoplastic polyester, a thermoplastic polyamide, a thermoplasticpolyolefin, or any combination thereof, as is described in greaterdetail below. The elastomeric material can be attached (e.g., affixed,coupled, adhered, bonded, etc.) to a surface of the substrate that isexternally-facing, such that the elastomeric material defines at least aportion of an externally-facing surface of the article or component ofthe article.

The substrate 25 can comprise or be a textile, including a knit textile,a woven textile, a non-woven textile, a braided textile, a crochetedtextile, or any combination thereof. The textile can comprise aplurality of fibers, one or more yarns, or both. The plurality of fibersor the one or more yarns or both can include one or more natural orsynthetic fibers or yarns. The synthetic fibers or yarns can comprise,consist of, or consist essentially of a thermoplastic composition. Thepolymeric component of the thermoplastic composition may comprise,consist of, or consist essentially of a thermoplastic polyurethane(TPU), a thermoplastic polyamide, a thermoplastic polyester, athermoplastic polyolefin, or a mixture thereof, as described in moredetail herein.

In another example, the component or article itself 15, or the segmentincluding the elastomeric material 16 can comprise a plurality offibers, one or more yarns, one or more textiles, or any combinationthereof. The plurality of fibers, the one or more yarns, the one or moretextiles, or any combination thereof, can act as a filler or as areinforcing element in one or more layers of the component or article 15or segment 16. The one or more textiles can comprise a knit textile, awoven textile, a non-woven textile, a braided textile, a crochetedtextile, or any combination thereof. The plurality of fibers, the one ormore yarns, the one or more textiles, or any combination thereof, can bepresent in the composition and the elastomeric material, or in a layerof the component or article 15 or segment 16, or in any combinationthereof. When present in a layer, the layer can be a composite layer, inwhich the plurality of fibers are dispersed in the composition of thelayer or elastomeric material of the layer, or in which the elastomericmaterial or the composition infiltrates a yarn and/or a textile andconsolidates the fibers of the yarn and/or the fibers or yarn of thetextile. For example, a layer can be a composite layer comprising afirst plurality of fibers dispersed in the elastomeric material. Inanother example, the elastomeric material can be a composite layercomprising a textile, wherein the elastomeric material infiltrates gapsbetween fibers and/or yarns of the textile, and substantially surroundsthe fibers and/or yarns of the textile. The plurality of fibers, the oneor more yarns, the one or more textiles, or any combination thereof, mayinclude one or more natural or synthetic fibers or yarns. The syntheticfibers or yarns may comprise, consist of, or consist essentially of athermoplastic composition. The polymeric component of the thermoplasticcomposition may comprise, consist of, or consist essentially of athermoplastic polyurethane (TPU), a thermoplastic polyamide, athermoplastic polyester, a thermoplastic polyolefin, or a mixturethereof, which are described in detail herein.

Optionally, the component may further include an adhesive, a primer, atie layer, or a combination thereof located between the second surface20 of the elastomeric material and the externally-facing side of thesubstrate 25 attached thereto. The adhesive, tie layer, or primer maycomprise, but not be limited to, a polymer having one or more epoxysegments, urethane segments, acrylic segments, cyanoacrylate segments,silicone segments, or a combination thereof. The adhesive, primer, ortie layer can include a thermoplastic polyurethane. Alternatively, theinterface between the second surface 20 of the elastomeric material andthe externally-facing side of the substrate 25 can be substantially freeof an adhesive, a primer, a tie layer, or any combination thereof.

At least a portion of the first surface 10 of the component 15 maycomprise a pattern or a texture. This pattern may represent a treadpattern. In addition to a pattern or texture, the first surface 10 ofthe component 15 may comprise one or more traction elements (best shownin FIG. 2G). In some examples, the portion of the elements that contactthe ground during use (e.g., the terminal end) are substantially free ofthe polymeric hydrogel or the elastomeric material including thepolymeric hydrogel as described herein, as, due to the lubricious natureof these material, they may reduce the effectiveness of the tractionelements. Alternatively, the portion of the traction elements whichcontact the ground during use can be made of a different material, suchas a material that is harder than the elastomeric material. Whendesirable, the one or more traction elements may have a conical orrectangular shape as further described below.

Referring now to FIGS. 2A to 2G, the finished article 1 may be, withoutlimitation, an article of apparel, such as a garment 50, or an articleof sporting equipment, such as a ball cap or helmet 55, footwear 75; atire or wheel 60; hunting, hiking, or camping equipment 65; a ball,glove, bat, club, or protective gear 70. Alternatively, the component 15may be attached to, coupled with, or in contact with another material,e.g., the substrate 25 of the finished article 1. The component 15 ofthe article of footwear 75 may be an outsole 15, for example (see FIGS.2F & 2G).

Referring now to FIGS. 2F and 2G, the footwear 75 or shoe 75 maycomprise, consist of, or consist essentially of an upper 25 and anoutsole 15 having a predetermined shape. The outsole 15 is in contactwith and affixed or attached to the upper 25. At least part of theoutsole 15 comprises an elastomeric material in an at least partiallycured state, alternatively, in a fully cured state. The elastomericmaterial or layer in the outsole 15 is a mixture of the polymerichydrogel and the cured rubber as described above and further definedherein. The polymeric hydrogel resin may exhibit a water uptake capacityin the range of 50 percent to 1200 percent, the water uptake capacityrepresenting the amount of water by weight taken up by the polymerichydrogel as a percentage by weight of dry hydrophilic resin. The curedrubber in the elastomeric material comprises one or more natural orsynthetic rubbers. The polymeric hydrogel is present in an amount thatranges from about 5 weight percent to about 75 weight percent based onthe overall weight of the elastomeric material. The elastomeric materialmay further comprise one or more processing aids independently selectedfrom the group of crosslinking agents, plasticizers, mold releaseagents, lubricants, antioxidants, flame retardants, dyes, pigments,reinforcing and non-reinforcing fillers, fiber reinforcements, and lightstabilizers.

Still referring to FIGS. 2F and 2G, the outsole 15 refers to the verybottom of the article of footwear 75 such that one surface 10 is facingthe ground during wear. The outsole 15 can exhibit a thickness that isin the range from about 0.2 millimeters to about 2.0 millimeters;alternatively, about 0.2 millimeters to about 1.0 millimeters. Theoutsole 15 may be relatively smooth or include a tread pattern 90. Thesurface 10 of the outsole 15 may directly contact the ground duringwear. Optionally, the outsole 15 may also include one or more tractionelements 95. When the outsole 15 includes traction elements 95, thetraction elements 95 may directly contact the ground during wear, whilethe surface 10 of the outsole may only contact the ground when theground is sufficiently soft that an entire height of the tractionelements 95 sink into the ground during wear. The traction elements 95may provide enhanced traction, as well as provide support or flexibilityto the outsole 15 and/or provide an aesthetic design or look to theshoe.

The traction elements 95 may include, but are not limited to, variousshaped projections, such as cleats, studs, spikes, or similar elementsconfigured to enhance traction for a wearer during cutting, turning,stopping, accelerating, and backward movement as described in moredetail herein. The traction elements 95 can be arranged in any suitablepattern along the bottom surface of the outsole 15. For instance, thetraction 95 elements can be distributed in groups or clusters along theoutsole 15 (e.g., clusters of 2-8 traction elements). Alternatively, thetraction elements 95 can be arranged along the outsole 15 symmetricallyor non-symmetrically between a medial side and a lateral side of thearticle of footwear 1. Moreover, one or more of the traction elementscan be arranged along a centerline of the outsole 15 between the medialside and the lateral side.

The traction elements 95 can be made of one or more materials that aredifferent from the composition and/or elastomeric material. Whendesirable, the traction elements 95 may be individually selected to becomprised of the same rubber as is present in the composition and/or theelastomeric material. Alternatively, the traction elements 95 cancomprise a different rubber (e.g., a harder rubber) or a differentpolymeric material (e.g., a different type of cured rubber, or apolymeric material substantially free of natural or synthetic rubber).In at least one of the traction elements 95 the portion of said elementthat makes contact with the ground may be substantially free of thecomposition or elastomeric material. The one or more traction elements95 may be made of a polymeric material that is harder than theelastomeric material. A plurality of traction elements can be presentwith at least two of the plurality of traction elements differing fromeach other based on height, width, or thickness.

In another aspect, FIGS. 3A and 3B illustrates an article of footwear100 that includes an upper 120 and a sole structure 130, where the upper120 is secured to the sole structure 130. The sole structure 130 caninclude a toe plate 132, a mid-plate 134, and a heel plate 136 andtraction elements 138 as well as the elastomeric material 110, where theelastomeric material 100 is on the outside surface so to beground-facing under normal use. Optionally, the elastomeric material 110can be an externally-facing layer of the upper 120. The elastomericmaterial 110 can cover substantially all of the upper 120 or can be in aregion proximal to the sole structure 130. In other aspects notdepicted, the sole structure 130 may incorporate foam, one or morefluid-filled chambers, plates, moderators, or other elements thatfurther attenuate forces, enhance stability, or influence the motions ofthe foot.

The upper 120 of the footwear 100 has a body which may be fabricatedfrom materials known in the art for making articles of footwear, and isconfigured to receive a user's foot. The upper 120 and components of theupper 120 may be manufactured according to conventional techniques(e.g., molding, extrusion, thermoforming, stitching, knitting, etc.).The upper 120 may alternatively have any desired aesthetic design,functional design, brand designators, and the like.

The sole structure 130 may be directly or otherwise secured to the upper120 using any suitable mechanism or method. As used herein, the terms“secured to”, such as for an outsole that is secured to an upper, e.g.,is operably secured to an upper, refers collectively to directconnections, indirect connections, integral formations, and combinationsthereof. For instance, for the sole structure 130 that is secured to theupper 120, the sole structure 130 can be directly connected to the upper120 using the hot melt adhesive layer of the elastomeric material andoptionally include the outsole 120 indirectly connected to the upper(e.g., with an intermediate midsole), can be integrally formed with theupper (e.g., as a unitary component), and combinations thereof.

FIGS. 4A and 4B illustrate cross-sections of an article of footwear 200and 201 that include an outsole including the elastomeric material orthe composition of the present disclosure in a first layer 204. FIG. 4Aillustrates a cross-section of an article of footwear 200 including thefirst layer 204 attached (optionally) to the upper 202 and a secondlayer 206 (or structure or substrate or film) comprising a cured rubbersubstantially free of the polymeric hydrogel, for example a cured rubbersuch as rubber lugs, rubber cleats, or other tractions elements. Theoutsole can be prepared by forming the first layer 204 of an uncuredcomposition or partially cured elastomeric material of the presentdisclosure, forming the second layer 206 of an uncured or partiallyrubber, then placing a first side of the first layer 204 in contact witha first side of the second layer 206, and fully curing the first layer204 and the second layer 206 while they remain in contact with eachother. For example, they can be cured in a vulcanization process. Inthis example, the curing process results in a portion of the rubber ofthe first layer 204 crosslinking with a portion of the rubber of thesecond layer 206, forming chemical bonds (e.g., crosslinking) whichadhere the first layer 204 and the second layer 206 to each otherwithout an adhesive. In particular, during a curing process, the rubberin the first layer 204 can crosslink with the rubber in the second layer206 and the polymeric hydrogel of the first layer 204 can optionallycrosslink with the rubber in the first layer 204 and/or the rubber inthe second layer 206. In this way, the first layer 204 and the secondlayer 206 can form stronger bonds than what might be obtained usingadhesives or the like. In an embodiment, the second layer 206 can bedisposed in a mold (not shown) and then the first layer 204 disposed ontop of the second layer 206. The first layer 206 and the second layer204 can be subjected to a vulcanization process to form the outsole. Theupper 202 or a component of the upper can be optionally disposed on asecond side of the first layer 204 before or after vulcanization, asillustrated in FIG. 4A, or a midsole or plate 208 can be disposedbetween the upper 202 (optionally including a strobel) and the outsolecan be bonded to the midsole or plate using a direct attachment processby forming the midsole or plate 208 in contact with the outsole, or byattaching the midsole or plate 208 using an adhesive or other attachmentmethod.

The term “externally-facing” as used in “externally-facing layer” refersto the position the element is intended to be in when the element ispresent in an article during normal use. If the article is footwear, theelement is positioned toward the ground during normal use (i.e., isground-facing) by a wearer when in a standing position, and thus maycontact the ground including unpaved surfaces when the footwear is usedin a conventional manner, such as standing, walking or running on anunpaved surface. In other words, even though the element may notnecessarily be facing the ground during various steps of manufacturingor shipping, if the element is intended to face the ground during normaluse by a wearer, the element is understood to be externally-facing ormore specifically for an article of footwear, ground-facing. In somecircumstances, due to the presence of elements such as tractionelements, the externally-facing (e.g., ground-facing) surface can bepositioned toward the ground during conventional use but may notnecessarily come into contact the ground. For example, on hard ground orpaved surfaces, the terminal ends of traction elements on the outsolemay directly contact the ground, while portions of the outsole locatedbetween the traction elements do not. As described in this example, theportions of the outsole located between the traction elements areconsidered to be externally-facing (e.g., ground-facing) even thoughthey may not directly contact the ground in all circumstances.

The traction elements may each include any suitable cleat, stud, spike,or similar element configured to enhance traction for a wearer duringcutting, turning, stopping, accelerating, and backward movement. Thetraction elements can be arranged in any suitable pattern along thebottom surface of the footwear. For instance, the traction elements canbe distributed in groups or clusters along the outsole (e.g., clustersof 2-8 traction elements). In an aspect, the traction elements can begrouped into a cluster at the forefoot region, a cluster at the midfootregion, and a cluster at the heel region. In this example, six of thetraction elements are substantially aligned along the medial side of theoutsole, and the other six traction elements are substantially alignedalong the lateral side of the outsole.

The traction elements may alternatively be arranged along the outsolesymmetrically or non-symmetrically between the medial side and thelateral side, as desired. Moreover, one or more of the traction elementsmay be arranged along a centerline of outsole between the medial sideand the lateral side, such as a blade, as desired to enhance orotherwise modify performance.

Alternatively (or additionally), traction elements can also include oneor more front-edge traction elements, such as one or more blades, one ormore fins, and/or one or more cleats (not shown) secured to (e.g.,integrally formed with) the backing plate at a front-edge region betweenforefoot region and cluster. In this application, the externally-facingportion of the elastomeric material can optionally extend across thebottom surface at this front-edge region while maintaining good tractionperformance.

Furthermore, the traction elements may each independently have anysuitable dimension (e.g., shape and size). For instance, in somedesigns, each traction element within a given cluster (e.g., clusters)may have the same or substantially the same dimensions, and/or eachtraction element across the entirety of the outsole may have the same orsubstantially the same dimensions. Alternatively, the traction elementswithin each cluster may have different dimensions, and/or each tractionelement across the entirety of the outsole may have differentdimensions.

Examples of suitable shapes for the traction elements includerectangular, hexagonal, cylindrical, conical, circular, square,triangular, trapezoidal, diamond, ovoid, as well as other regular orirregular shapes (e.g., curved lines, C-shapes, etc.). The tractionelements may also have the same or different heights, widths, and/orthicknesses as each other, as further discussed below. Further examplesof suitable dimensions for the traction elements and their arrangementsalong the plate include those provided in soccer/global footballfootwear commercially available under the tradenames “TIEMPO”,“HYPERVENOM”, “MAGISTA”, and “MERCURIAL” from Nike, Inc. of Beaverton,Oreg., USA.

The traction elements may be incorporated into the outsole including theoptional backing plate by any suitable mechanism such that the tractionelements preferably extend from the bottom surface (e.g., elastomericmaterial). For example, as discussed below, the traction elements may beintegrally formed with the backing plate through a molding process(e.g., for firm ground (FG) footwear). Alternatively, the outsole oroptional backing plate may be configured to receive removable tractionelements, such as screw-in or snap-in traction elements. In theseaspects, the backing plate may include receiving holes (e.g., threadedor snap-fit holes, not shown), and the traction elements can be screwedor snapped into the receiving holes to secure the traction elements tothe backing plate (e.g., for soft ground (SG) footwear).

In further examples, a first portion of the traction elements can beintegrally formed with the outsole or optional backing plate and asecond portion of the traction elements can be secured with screw-in,snap-in, or other similar mechanisms (e.g., for SG pro footwear). Thetraction elements may also be configured as short studs for use withartificial ground (AG) footwear, if desired. In some applications, thereceiving holes may be raised or otherwise protrude from the generalplane of the bottom surface of the backing plate. Alternatively, thereceiving holes may be flush with the bottom surface.

The traction elements can be fabricated from any suitable material foruse with the outsole. For example, the traction elements may include oneor more of polymeric materials such as thermoplastic elastomers;thermoset polymers; elastomeric polymers; silicone polymers; natural andsynthetic rubbers; composite materials including polymers reinforcedwith carbon fiber and/or glass; natural leather; metals such asaluminum, steel and the like; and combinations thereof. In aspects inwhich the traction elements are integrally formed with the backing plate(e.g., molded together), the traction elements preferably include thesame materials as the outsole or backing plate (e.g., thermoplasticmaterials). Alternatively, in aspects in which the traction elements areseparate and insertable into receiving holes of the backing plate, thetraction elements can include any suitable materials that can secured inthe receiving holes of the backing plate (e.g., metals and thermoplasticmaterials).

As mentioned above, the traction element may have any suitabledimensions and shape, where the shaft (and the outer side surface) cancorrespondingly have rectangular, hexagonal, cylindrical, conical,circular, square, triangular, trapezoidal, diamond, ovoid, as well asother regular or irregular shapes (e.g., curved lines, C-shapes, etc.).Similarly, the terminal edge can have dimensions and sizes thatcorrespond to those of the outer side surface, and can be substantiallyflat, sloped, rounded, and the like. Furthermore, in some aspects, theterminal edge can be substantially parallel to the bottom surface and/orthe elastomeric material.

Examples of suitable average lengths for each shaft relative to bottomsurface range from 1 millimeter to 20 millimeters, from 3 millimeters to15 millimeters, or from 5 millimeters to 10 millimeters, where, asmentioned above, each traction element can have different dimensions andsizes (i.e., the shafts of the various traction elements can havedifferent lengths).

It has been found the elastomeric material and articles incorporatingthe elastomeric material (e.g., footwear) can prevent or reduce theaccumulation of soil on the externally-facing layer of the elastomericmaterial during wear on unpaved surfaces. As used herein, the term“soil” can include any of a variety of materials commonly present on aground or playing surface and which might otherwise adhere to an outsoleor exposed midsole of a footwear article. Soil can include inorganicmaterials such as mud, sand, dirt, and gravel; organic matter such asgrass, turf, leaves, other vegetation, and excrement; and combinationsof inorganic and organic materials such as clay. Additionally, soil caninclude other materials such as pulverized rubber which may be presenton or in an unpaved surface.

While not wishing to be bound by theory, it is believed that thepolymeric hydrogel of the elastomeric material, as well as theelastomeric material of the present disclosure itself, when sufficientlywet with water (including water containing dissolved, dispersed orotherwise suspended materials) can provide compressive compliance and/orexpulsion of uptaken water. In particular, it is believed that thecompressive compliance of the wet polymeric hydrogel and/or elastomericmaterial, the expulsion of liquid from the wet polymeric hydrogel and/orelastomeric material, a change in topography of the externally-facingsurface, or combination thereof, can disrupt the adhesion of soil on orat the externally-facing surface, or the cohesion of the particles toeach other on the externally-facing surface, or can disrupt both theadhesion and cohesion. This disruption in the adhesion and/or cohesionof soil is believed to be a responsible mechanism for preventing (orotherwise reducing) the soil from accumulating on the externally-facingsurface (due to the presence of the wet material).

This disruption in the adhesion and/or cohesion of soil is believed tobe a responsible mechanism for preventing (or otherwise reducing) thesoil from accumulating on the externally-facing surface (due to thepresence of the polymeric hydrogel in the elastomeric material of thepresent disclosure). As can be appreciated, preventing soil fromaccumulating on articles, including on articles of footwear, apparel orsporting equipment particularly, can improve the performance of tractionelements present on the articles (e.g., on a sole) during use or wear onunpaved surfaces, can prevent the article from gaining weight due toaccumulated soil during use or wear, can preserve performance of thearticle and thus can provide significant benefits to a user or wearer ascompared to an article without the elastomeric material present.

The swelling of the elastomeric material can be observed as an increasein thickness of the elastomeric material from the dry-state thickness ofthe elastomeric material, through a range of intermediate-statethicknesses as additional water is absorbed, and finally to asaturated-state thickness of the elastomeric material, which is anaverage thickness of the elastomeric material when fully saturated withwater. For example, the saturated-state thickness (or length, and/orheight) for the fully saturated elastomeric material can be greater than25 percent, greater than 50 percent, greater than 100 percent, greaterthan 150 percent, greater than 200 percent, greater than 250 percent,greater than 300 percent, greater than 350 percent, greater than 400percent, or greater than 500 percent, of the dry-state thickness for thesame elastomeric material, as characterized by the Swelling CapacityTest. The saturated-state thickness (or length, and/or height) for thefully saturated elastomeric material can be about 150 percent to 500percent, about 150 percent to 400 percent, about 150 percent to 300percent, or about 200 percent to 300 percent of the dry-state thicknessfor the same elastomeric material. The increase in thickness may begreater in areas at and/or near the channel where the elastomericmaterial is exposed through the channel.

The polymeric hydrogel and/or the elastomeric material in neat form canhave an increase in thickness (or length, and/or height) at 1 hour ofabout 35 percent to 400 percent, about 50 percent to 300 percent, orabout 100 percent to 200 percent, as characterized by the SwellingCapacity Test. The elastomeric material in neat form can have anincrease in thickness (or length, and/or height) at 24 hours of about 45percent to 500 percent, about 100 percent to 400 percent, or about 150percent to 300 percent. Correspondingly, the component or layercomprising the elastomeric material can have an increase in volume at 1hour of about 50 percent to 500 percent, about 75 percent to 400percent, or about 100 percent to 300 percent.

The polymeric hydrogel and/or the elastomeric material can quickly takeup water that is in contact with the polymeric hydrogel and/or theelastomeric material. For instance, the elastomeric material can take upwater from mud and wet grass, such as during a warmup period prior to acompetitive match. Alternatively (or additionally), the elastomericmaterial can be pre-conditioned with water so that the elastomericmaterial of the elastomeric material is partially or fully saturated,such as by spraying or soaking the structure with water prior to use.

The elastomeric material can exhibit an overall water uptake capacity ofabout 10 weight percent to 225 weight percent as measured in the WaterUptake Capacity Test over a soaking time of 24 hours using the ComponentSampling Procedure, as will be defined below. The overall water uptakecapacity (at 24 hours) exhibited by the elastomeric material can be inthe range of about 10 weight percent to about 225 weight percent; about30 weight percent to about 200 weight percent; about 50 weight percentto about 150 weight percent; or about 75 weight percent to about 125weight percent. The water uptake capacity, as measured by the WaterUptake Capacity test at 24 hours, exhibited by the elastomeric materialcan be about 20 weight percent or more, about 40 weight percent or more,about 60 weight percent or more, about 80 weight percent or more, orabout 100 weight percent or more. For the purpose of this disclosure,the term “overall water uptake capacity” is used to represent the amountof water by weight taken up by the elastomeric material as a percentageby weight of the elastomeric material when dry. The procedure formeasuring overall water uptake capacity includes measurement of the“dry” weight of the elastomeric material, immersion of the elastomericmaterial in water at ambient temperature (˜23° C.) for a predeterminedamount of time, followed by re-measurement of the weight of theelastomeric material when “wet”. The procedure for measuring the overallweight uptake capacity according to the Water Uptake Capacity Test usingthe Component Sampling Procedure is described below.

The polymeric hydrogel itself, in neat form (e.g., prior to beingdistributed in the rubber), can exhibit an overall water uptake capacityof about 10 weight percent to 3000 weight percent as measured in theWater Uptake Capacity Test over a soaking time of 24 hours using theComponent Sampling Procedure, as will be defined below. The overallwater uptake capacity (at 24 hours) exhibited by the polymeric hydrogelcan be in the range of about 50 weight percent to about 2500 weightpercent; about 100 weight percent to about 2000 weight percent; about200 weight percent to about 1500 weight percent; or about 300 weightpercent to about 1000 weight percent. The water uptake capacity, asmeasured by the Water Uptake Capacity test at 24 hours, exhibited by thepolymeric hydrogel can be about 20 weight percent or more, about 40weight percent or more, about 60 weight percent or more, about 80 weightpercent or more, or about 100 weight percent or more. The water uptakecapacity, as measured by the Water Uptake Capacity test at 24 hours,exhibited by the polymeric hydrogel can be about 100 weight percent ormore, about 200 weight percent or more, about 300 weight percent ormore, about 400 weight percent or more, or about 500 weight percent ormore. For the purpose of this disclosure, the term “overall water uptakecapacity” is used to represent the amount of water by weight taken up bythe polymeric hydrogel as a percentage by weight of the polymerichydrogel when dry. The procedure for measuring overall water uptakecapacity includes measurement of the “dry” weight of the polymerichydrogel, immersion of the polymeric hydrogel in water at ambienttemperature (˜23° C.) for a predetermined amount of time, followed byre-measurement of the weight of the polymeric hydrogel when “wet”. Theprocedure for measuring the overall weight uptake capacity according tothe Water Uptake Capacity Test using the Component Sampling Procedure isdescribed below.

The elastomeric material can have a “time value” equilibrium wateruptake capacity, where the time value corresponds to the duration ofsoaking or exposure to water (e.g., for example in use of footwear beingexposed to water). For example, a “30 second equilibrium water uptakecapacity” corresponds to the water uptake capacity at a soaking durationof 30 seconds, a “2 minute equilibrium water uptake capacity”corresponds to the water uptake capacity at a soaking duration of 2minutes, and so on at various time duration of soaking. A time durationof “0 seconds” refers to the dry-state and a time duration of 24 hourscorresponds to the saturated state of the elastomeric material at 24hours. Additional details are provided in the Water Uptake Capacity TestProtocol described herein.

The polymeric hydrogel can have a “time value” equilibrium water uptakecapacity, where the time value corresponds to the duration of soaking orexposure to water (e.g., in neat form when exposed to water). Forexample, a “30 second equilibrium water uptake capacity” corresponds tothe water uptake capacity at a soaking duration of 30 seconds, a “2minute equilibrium water uptake capacity” corresponds to the wateruptake capacity at a soaking duration of 2 minutes, and so on at varioustime duration of soaking. A time duration of “0 seconds” refers to thedry-state and a time duration of 24 hours corresponds to the saturatedstate of the polymeric hydrogel at 24 hours. Additional details areprovided in the Water Uptake Capacity Test Protocol described herein.

The elastomeric material can also be characterized by a water uptakerate of 10 g/m²√min to 120 g/m²√min as measured in the Water Uptake RateTest using the Material Sampling Procedure. The water uptake rate isdefined as the weight (in grams) of water absorbed per square meter (m²)of the elastomeric material over the square root of the soaking time(min). Alternatively, the water uptake rate ranges from about 12g/m²/min to about 100 g/m²/min; alternatively, from about 25 g/m²/min toabout 90 g/m²/min; alternatively, up to about 60 g/m²/min.

To cause a character change (e.g., shape, color, etc.) of theelastomeric material, the elastomeric material can have a water uptakerate of 10 g/m²/min to 120 g/m²/min as measured in the Water Uptake RateTest using the Material Sampling Procedure

The polymeric hydrogel can also be characterized by a water uptake rateof 10 g/m²/min to 120 g/m²/min as measured in the Water Uptake Rate Testusing the Material Sampling Procedure. The water uptake rate is definedas the weight (in grams) of water absorbed per square meter (m²) of thepolymeric hydrogel over the square root of the soaking time (min).Alternatively, the water uptake rate ranges from about 12 g/m²/min toabout 100 g/m²/min; alternatively, from about 25 g/m²/min to about 90g/m²/min; alternatively, up to about 60 g/m²/min.

To cause a character change of the elastomeric material, the polymerichydrogel present in the composition used to form the elastomericmaterial can have a water uptake rate of 10 g/m²/min to 120 g/m²/min asmeasured in the Water Uptake Rate Test using the Material SamplingProcedure.

The overall water uptake capacity and the water uptake rate can bedependent upon the amount of the polymeric hydrogel that is present inthe elastomeric material. The polymeric hydrogel can characterized by awater uptake capacity of 50 weight percent to 2500 weight percent asmeasured according to the Water Uptake Capacity Test using the MaterialSampling Procedure. In this case, the water uptake capacity of thepolymeric hydrogel is determined based on the amount of water by weighttaken up by the polymeric hydrogel (in neat form) as a percentage byweight of dry polymeric hydrogel. Alternatively, the water uptakecapacity exhibited by the polymeric hydrogel is in the range of about100 weight percent to about 1500 weight percent; alternatively, in therange of about 300 weight percent to about 1200 weight percent.

To cause a character change of the elastomeric material, the polymerichydrogel present in the composition used to form the elastomericmaterial can have a water uptake capacity of 50 weight percent to 2500weight percent as measured according to the Water Uptake Capacity Testusing the Material Sampling Procedure.

The elastomeric material can exhibit no appreciable weight loss in aWater Cycling Test. The Water Cycling Test as further defined belowinvolves a comparison of the initial weight of the elastomeric materialto that of the elastomeric material after being soaked in a water bathfor a predetermined amount of time, dried and then reweighed.Alternatively, the elastomeric material exhibits a Water Cycling weightloss from 0 weight percent to about 15 weight percent as measuredpursuant to the Water Cycling Test and using the Material SamplingProcedure or the Component Sampling Procedure. Alternatively, the watercycling weight loss is less than 15 weight percent; alternatively, lessthan 10 weight percent.

The elastomeric material may also be characterized by the degree towhich it exhibits a mud pull-off force that is less than about 12 Newton(N). Alternatively, the mud pull-off force is less than about 10 N;alternatively, in the range of about 1 N to about 8 N. The mud pull-offforce is determined by the Mud Pull-Off Test using the ComponentSampling Procedure as described the Example section below.

The Component Sampling Procedure may constitute the Footwear SamplingProcedure, when the component is part of an article of footwear; theApparel Sampling Procedure, when the component is part of anotherarticle of apparel (e.g., a garment); or the Equipment SamplingProcedure, when the component is part of an article of sportingequipment. The Material Sampling Procedure is used when the sample isprovided in media form. Each of these sampling procedures are describedin more detail in the Example section provided below.

The surface of the elastomeric material can exhibit hydrophilicproperties. The hydrophilic properties can be characterized bydetermining the static sessile drop contact angle of the elastomericmaterial's surface. Accordingly, in some examples, the elastomericmaterial's surface in a dry state has a static sessile drop contactangle (or dry-state contact angle) of less than 105 degrees, or lessthan 95 degrees, less than 85 degrees, as characterized by the ContactAngle Test. The Contact Angle Test can be conducted on a sample obtainedin accordance with the Article Sampling Procedure or the Co-ExtrudedFilm Sampling Procedure. In some further examples, the elastomericmaterial in a dry state has a static sessile drop contact angle rangingfrom 60 degrees to 100 degrees, from 70 degrees to 100 degrees, or from65 degrees to 95 degrees.

In other examples, the surface of the elastomeric material in a wetstate has a static sessile drop contact angle (or wet-state contactangle) of less than 90 degrees, less than 80 degrees, less than 70degrees, or less than 60 degrees. In some further examples, the surfacein a wet state has a static sessile drop contact angle ranging from 45degrees to 75 degrees. In some cases, the dry-state static sessile dropcontact angle of the surface is greater than the wet-state staticsessile drop contact angle of the surface by at least 10 degrees, atleast 15 degrees, or at least 20 degrees, for example from 10 degrees to40 degrees, from 10 degrees to 30 degrees, or from 10 degrees to 20degrees.

The exposed region of the elastomeric material can also exhibit a lowcoefficient of friction when the elastomeric material is wet. Examplesof suitable coefficients of friction for the elastomeric material in adry state (or dry-state coefficient of friction) are less than 1.5, forinstance ranging from 0.3 to 1.3, or from 0.3 to 0.7, as characterizedby the Coefficient of Friction Test. The Coefficient of Friction Testcan be conducted on a sample obtained in accordance with the ArticleSampling Procedure, or the Co-Extruded Film Sampling Procedure. Examplesof suitable coefficients of friction for the elastomeric material in awet state (or wet-state coefficient of friction) are less than 0.8 orless than 0.6, for instance ranging from 0.05 to 0.6, from 0.1 to 0.6,or from 0.3 to 0.5. Furthermore, the elastomeric material can exhibit areduction in its coefficient of friction from its dry state to its wetstate, such as a reduction ranging from 15 percent to 90 percent, orfrom 50 percent to 80 percent. In some cases, the dry-state coefficientof friction is greater than the wet-state coefficient of friction forthe material, for example being higher by a value of at least 0.3 or0.5, such as 0.3 to 1.2 or 0.5 to 1.

Furthermore, the compliance of the elastomeric material can becharacterized based on the elastomeric material's storage modulus in thedry state (when equilibrated at 0 percent relative humidity (RH)), andin a partially wet state (e.g., when equilibrated at 50 percent RH or at90 percent RH), and by reductions in its storage modulus between the dryand wet states. In particular, the elastomeric material can have areduction in storage modulus (4E′) from the dry state relative to thewet state. A reduction in storage modulus as the water concentration inthe elastomeric material corresponds to an increase in compliance,because less stress is required for a given strain/deformation.

The elastomeric material can exhibit a reduction in the storage modulusfrom its dry state to its wet state (50 percent RH) of more than 20percent, more than 40 percent, more than 60 percent, more than 75percent, more than 90 percent, or more than 99 percent, relative to thestorage modulus in the dry state, and as characterized by the StorageModulus Test with the Neat Film Sampling Process.

In some further aspects, the dry-state storage modulus of theelastomeric material is greater than its wet-state (50 percent RH)storage modulus by more than 25 megaPascals (MPa), by more than 50 MPa,by more than 100 MPa, by more than 300 MPa, or by more than 500 MPa, forexample ranging from 25 MPa to 800 MPa, from 50 MPa to 800 MPa, from 100MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPa to 800 MPa, from25 MPa to 200 MPa, from 25 MPa to 100 MPa, or from 50 MPa to 200 MPa.Additionally, the dry-state storage modulus can range from 40 MPa to 800MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400 MPa, ascharacterized by the Storage Modulus Test. Additionally, the wet-statestorage modulus can range from 0.003 MPa to 100 MPa, from 1 MPa to 60MPa, or from 20 MPa to 40 MPa.

The elastomeric material can exhibit a reduction in the storage modulusfrom its dry state to its wet state (90 percent RH) of more than 20percent, more than 40 percent, more than 60 percent, more than 75percent, more than 90 percent, or more than 99 percent, relative to thestorage modulus in the dry state, and as characterized by the StorageModulus Test with the Neat Film Sampling Process. The dry-state storagemodulus of the elastomeric material can be greater than its wet-state(90 percent RH) storage modulus by more than 25 megaPascals (MPa), bymore than 50 MPa, by more than 100 MPa, by more than 300 MPa, or by morethan 500 MPa, for example ranging from 25 MPa to 800 MPa, from 50 MPa to800 MPa, from 100 MPa to 800 MPa, from 200 MPa to 800 MPa, from 400 MPato 800 MPa, from 25 MPa to 200 MPa, from 25 MPa to 100 MPa, or from 50MPa to 200 MPa. Additionally, the dry-state storage modulus can rangefrom 40 MPa to 800 MPa, from 100 MPa to 600 MPa, or from 200 MPa to 400MPa, as characterized by the Storage Modulus Test. Additionally, thewet-state storage modulus can range from 0.003 MPa to 100 MPa, from 1MPa to 60 MPa, or from 20 MPa to 40 MPa.

In addition to a reduction in storage modulus, the elastomeric materialcan also exhibit a reduction in its glass transition temperature fromthe dry state (when equilibrated at 0 percent relative humidity (RH) tothe wet state (when equilibrated at 90 percent RH). While not wishing tobe bound by theory, it is believed that the water taken up by theelastomeric material plasticizes the elastomeric material, which reducesits storage modulus and its glass transition temperature, rendering theelastomeric material more compliant (e.g., compressible, expandable, andstretchable).

The elastomeric material can exhibit a reduction in glass transitiontemperature (ΔT_(g)) from its dry-state (0 percent RH) glass transitiontemperature to its wet-state glass transition (90 percent RH)temperature of more than a 5 degrees C. difference, more than a 6degrees C. difference, more than a 10 degrees C. difference, or morethan a 15 degrees C. difference, as characterized by the GlassTransition Temperature Test with the Neat Film Sampling Process or theNeat Material Sampling Process. For instance, the reduction in glasstransition temperature can range from more than a 5 degrees C.difference to a 40 degrees C. difference, from more than a 6 degrees C.difference to a 50 degrees C. difference, form more than a 10 degrees C.difference to a 30 degrees C. difference, from more than a 30 degrees C.difference to a 45 degrees C. difference, or from a 15 degrees C.difference to a 20 degrees C. difference. The elastomeric material canalso exhibit a dry glass transition temperature ranging from −40 degreesC. to −80 degrees C., or from −40 degrees C. to −60 degrees C.

Alternatively (or additionally), the reduction in glass transitiontemperature can range from a 5 degrees C. difference to a 40 degrees C.difference, form a 10 degrees C. difference to a 30 degrees C.difference, or from a 15 degrees C. difference to a 20 degrees C.difference. The elastomeric material can also exhibit a dry glasstransition temperature ranging from −40 degrees C. to −80 degrees C., orfrom −40 degrees C. to −60 degrees C.

The total amount of water that the elastomeric material can take updepends on a variety of factors, such as its composition, when present,the type and concentration of polymeric hydrogel (e.g., itshydrophilicity), its cross-linking density, its thickness, the amount ofthe elastomeric material present in the elastomeric material, and thelike. The water uptake capacity and the water uptake rate of theelastomeric material, and of the elastomeric material, are dependent onthe size and shape of its geometry, and are typically based on the samefactors. Conversely, the water uptake rate is transient and can bedefined kinetically. The three factors for water uptake rate for a givenelastomeric material present in a given elastomeric material having agiven geometry include time, thickness, and the surface area of theexposed region available for taking up water.

As also mentioned above, in addition to swelling, the compliance of theelastomeric material can also increase from being relatively stiff(i.e., dry-state) to being increasingly stretchable, compressible, andmalleable (i.e., wet-state). The increased compliance accordingly canallow the elastomeric material to readily compress under an appliedpressure (e.g., during a foot strike on the ground), and in someexamples, to quickly expel at least a portion of its retained water(depending on the extent of compression). While not wishing to be boundby theory, it is believed that this compressive compliance alone, waterexpulsion alone, or both in combination can disrupt the adhesion and/orcohesion of soil, which prevents or otherwise reduces the accumulationof soil.

In addition to quickly expelling water, in particular examples, thecompressed elastomeric material is capable of quickly re-absorbing waterwhen the compression is released (e.g., liftoff from a foot strikeduring normal use). As such, during use in a wet or damp environment(e.g., a muddy or wet ground), the elastomeric material of the structurecan dynamically expel and repeatedly take up water over successive footstrikes, particularly from a wet surface. As such, elastomeric materialof the structure can continue to prevent soil accumulation over extendedperiods of time (e.g., during an entire competitive match), particularlywhen there is ground water available for re-uptake, as well as undergo acharacter change and be aesthetically advantageous.

As used herein, the terms “take up”, “taking up”, “uptake”, “uptaking”,and the like refer to the drawing of a liquid (e.g., water) from anexternal source into the elastomeric material, the elastomeric material,and when present, the polymeric hydrogel, such as by absorption,adsorption, or both. Furthermore, as briefly mentioned above, the term“water” refers to an aqueous liquid that can be pure water, or can be anaqueous carrier with lesser amounts of dissolved, dispersed or otherwisesuspended materials (e.g., particulates, other liquids, and the like).

In addition to being effective at preventing soil accumulation, theelastomeric material has also been found to be sufficiently durable forits intended use on the ground-contacting side of the article offootwear. In various aspects, the useful life of the elastomericmaterial (and footwear containing it) is at least 10 hours, 20 hours, 50hours, 100 hours, 120 hours, or 150 hours of wear.

Having described the article, composition and elastomeric materials ingeneral, additional details regarding articles, compositions andelastomeric materials are now provided. The article can include theelastomeric material, wherein, in the elastomeric material, thepolymeric hydrogel is distributed throughout the cured rubber. At leasta portion (e.g. about 1 to 100 weight percent or about 50 to 100 weightpercent) of the polymeric hydrogel present in the elastomeric materialis entrapped by the cured rubber. The polymeric hydrogel can bephysically entrapped and/or chemically bonded to the cured rubber.

In an example, the footwear includes an upper and an outsole comprisinga first region having a first elastomeric material. The firstelastomeric material can include a mixture of a first cured rubber and afirst polymeric hydrogel. The first region defines a first portion of anexternally facing side of the outsole. The outsole also comprises asecond region having a second material, where the first region and thesecond region are adjacent one another. The second region defines asecond portion of the externally facing side of the outsole. Optionally,the second material is a second elastomeric material including a mixtureof a second cured rubber and a second polymeric hydrogel. Alternatively,the second material is a second cured rubber which is substantially freeof a polymeric hydrogel. The first polymeric hydrogel and the secondpolymeric hydrogel can be the same (e.g., the two polymeric hydrogelscan be formed of the same type of polymer or combination of polymershaving substantially equivalent water uptakes and are present in theelastomeric materials in substantially equivalent concentrations) orthey can be different (e.g., they can be formed of different types ofpolymer, and/or have substantially different water uptakes, and/or bepresent in the elastomeric materials in substantially differentconcentrations). Similarly, the cured rubber of the first elastomericmaterial and second elastomeric material can be the same (e.g., the twocured rubbers are formed of the same type of uncured rubber orcombination of uncured rubber having substantially equivalent molecularweights and are present in substantially equivalent concentrations) orthey can be different (e.g., they are formed from types of uncuredrubbers having different chemical structures and/or are present insubstantially different concentrations).

As described herein, an article can include two or more different typesof elastomeric materials, where each have different water uptakecapacities so that different physical characteristics are exhibited bythe different types of elastomeric materials. For example, when anarticle includes a first and a second elastomeric material that are inthe dry-state, the first and second elastomeric materials can havesubstantially physical characteristics.

The first elastomeric material can comprise a first colorant at a firstconcentration, where the type of colorant and/or the concentration ofthe colorant can be the same or different than a second elastomericmaterial. The first colorant and the second colorant can be the same ordifferent and can have substantially the same or differentconcentration, where differences in the elastomeric material can beresponsible for differences in a characteristic change of theelastomeric materials.

The rubber (e.g., uncured rubber, partially cured rubber, or curedrubber) of the composition and/or the elastomeric material can includeone or more natural and/or synthetic rubbers. The natural or syntheticrubbers can include: butadiene rubber, styrene-butadiene (SBR) rubber,butyl rubber, isoprene rubber, urethane rubber (e.g., millable), nitrilerubber, neoprene rubber, ethylene propylene diene monomer (EPDM) rubber,ethylene-propylene rubber, urethane rubber or any combination thereof.Other examples of rubber compounds include, but are not limited topolynorbornene rubber, methyl methacrylate butadiene styrene rubber(MBS), styrene ethylene butylene (SEBS) rubber, silicone rubber,urethane rubber, and mixtures thereof. The natural or synthetic rubbersmay be individually selected as virgin materials, regrind materials, ora mixture thereof.

The uncured rubber can be a millable rubber, such as a millablepolyurethane rubber. The millable rubber may be a thermally curablemillable rubber, such as a thermally curable millable polyurethanerubber, for example, a sulfur or peroxide curable millable rubber. Themillable rubber may also be a UV curable polyurethane rubber such as,for example, MILLATHANE UV-curable millable polyurethane rubber (TSEIndustries Inc., Clearwater, Fla., USA). The millable polyurethanerubber may be made be reacting either polyester or polyether polyolswith diisocyanates, such as methylene diphenyl diisocyanate (MDI) ortoluene diisocyanate (TDI), with or without a chain extender.

The rubber further can include an additive. For example, the additivecan include a plurality of polymer chains individually having a maleicanhydride moiety grafted to the polymer chain. The additive can be afunctionalized polymer which has been modified by grafting maleicanhydride groups into the polymer backbone, end groups, or side groups,including ethylene-based polymers with maleic anhydride grafting. Theadditive can be a maleic-anhydride modified polymer such as “FUSABOND”(sold by E. I. du Pont de Nemours and Company, Wilmington, Del., USA).The functionalized polymer can include modified ethylene acrylate carbonmonoxide terpolymers, ethylene vinyl acetates (EVAs), polyethylenes,metallocenepolyethylenes, ethylene propylene rubbers and polypropylenes,where the modification to the functional polymer can include maleicanhydride grafted to the functional polymer. The amount of the additivepresent in the uncured rubber formulation can be up to 10 parts perhundred resin (phr), or from about 1 phr to about 8 phr, or from about 3phr to about 6 phr.

The rubber can further comprise fillers; process oils; and/or a curingpackage including at least one of crosslinking agents(s), crosslinkingaccelerator(s), and crosslinking retarder(s). Examples of fillersinclude, but are not limited to, carbon black, silica, and talc.Examples of process oils include, but are not limited to, paraffin oiland/or aromatic oils. Examples of crosslinking agents include, but arenot limited to sulfur or peroxide initiators such as di-t-amyl peroxide,di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide (DCP),di(2-methyl-1-phenyl-2-propyl)peroxide, t-butyl2-methyl-1-phenyl-2-propyl peroxide,di(t-buylperoxy)-diisopropylbenzene,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,4,4-di(t-butylperoxy)-n-butylvalerate, and mixtures thereof. Examples ofcrosslinking accelerators include, but are not limited to,N-cyclohexyl-2-benzothiazole sulfenamide (CBZ),N-oxydiethylene-2-benzothiazole sulfenamide,N,N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole,2-(2,4-dinitrophenyl)mercaptobenzothiazole,2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyldisulfide; guanidine compounds, such as diphenylguanidine (DPG),triphenylguanidine, diorthonitrileguanidine, orthonitrile biguanide anddiphenylguanidine phthalate; aldehyde amine compounds or aldehydeammonia compounds, such as acetaldehyde-aniline reaction product,butylaldehyde-aniline condensate, hexamethylenetetramine andacetaldehyde ammonia; imidazoline compounds, such as2-mercaptoimidazoline; thiourea compounds, such as thiocarbanilide,diethylthiourea, dibutylthiourea, trimethylthiourea anddiorthotolylthiourea; thiuram compounds, such as tetramethylthiurammonosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide,tetrabutylthiuram disulfide and pentamethylenethiuram tetrasulfide;dithioate compounds, such as zinc dimethyldithiocarbamate, zincdiethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zincethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodiumdimethyldithiocarbamate, selenium dimethyldithiocarbamate and telluriumdimethyldithiocarbamate; xanthate compounds, such as zincdibutylxanthogenate; and other compounds, such as zinc white. Examplesof crosslinking retarders include, but are not limited to,alkoxyphenols, catechols, and benzoquinones, and alkoxyphenols such as3,5-di-t-butyl-4-hydroxyanisol.

In the article or component of the article, the elastomeric materialand/or the rubber comprises at least some level of crosslinking, is atleast partially cured, and generally is fully cured. In the finishedarticle, the rubber is at least partially cured, and is generally fullycured. Or stated another way, in the elastomeric materials of thepresent disclosure, the rubber is at least partially cured. As usedherein, the term “partially cured” generally refers to a compound (e.g.,a rubber) having a relatively low crosslink density of less than orequal to 10⁻³ moles per cubic centimeter, or less than or equal to 10⁻⁵moles per cubic centimeter. For example, the partially cured elastomericmaterial can have from about 15 to about 1500 monomer units presentbetween crosslinks. Dynamic mechanical analysis (DMA) can be used todetermine the modulus plateau for the compound. In the region of themodulus plateau above the glass transition temperature of the compoundand below the melting point of the compound, the crosslink density isdirectly proportional to the modulus of the compound. As used herein,the term “cured” generally refers to a compound (e.g., a rubber) havinga relatively high crosslink density. For example, the crosslink densityof the cured compound can be at least 20 percent greater, or at least 30percent greater, or at least 50 percent greater than the crosslinkdensity of the uncured or partially cured composition.

Examples of crosslinking reactions include, but are not limited to,free-radical reactions, ionic reactions (both anionic and cationic),addition reactions, and metal salt reactions. Crosslinking reactions canbe initiated by actinic radiation, including thermal radiation, UVradiation, electron beam radiation, and other types of high energyradiations. The crosslinking reactions can occur during a vulcanizationprocess.

The term “partially cured” can denote the occurrence of at least about 1percent, alternatively, at least about 5 percent of the totalpolymerization required to achieve a substantially full cure. The term“fully cured” is intended to mean a substantially full cure in which thedegree of curing is such that the physical properties of the curedmaterial do not noticeably change upon further exposure to conditionsthat induce curing (e.g., temperature, pressure, presence of curingagents, etc.).

In regard to the polymeric hydrogel, the polymeric hydrogel isdistributed throughout the uncured rubber and/or the cured rubber in theelastomeric material. Upon curing of the uncured rubber, at least aportion of the polymeric hydrogel in the elastomeric material may beentrapped (e.g., physically entrapped and/or chemically) by the curedrubber. A portion of the polymeric hydrogel can optionally be chemically(e.g., covalently or ionically) bonded to the cured rubber in theelastomeric material or in an adjacent surface or structure.Substantially all of the polymeric hydrogel in the elastomeric materialcan be entrapped (e.g., physically or chemically) by the cured rubber.

The polymeric hydrogel is present in the composition and/or elastomericmaterial in an amount of about 0.5 weight percent to about 85 weightpercent based on the overall weight of the elastomeric material (i.e.,polymeric) component present in composition or the elastomeric material.Alternatively, the polymeric hydrogel is present in an amount thatranges from about 5 weight percent to about 80 weight percent based onthe overall weight of the composition or the elastomeric material;alternatively, about 10 weight percent to about 70 weight percent, orabout 20 weight percent to about 70 weight percent, or about 30 weightpercent to about 70 weight percent, or about 45 to about 70 weightpercent. Alternatively, concentration of the polymeric hydrogel in thecomposition and/or the elastomeric material can be expressed in partsper hundred resin (phr) based on the overall weight of the resincomponent of the composition or the elastomeric material. For example,the composition or elastomeric material can comprise from about 5 partsper hundred resin (phr), or about 10 to 80 phr, or about 15 to 70 phr,or about 20 to 70 phr, or about 30 to 70 phr, or about 45 to 70 phr ofthe polymeric hydrogel.

For the purpose of this disclosure, the term “weight” refers to a massvalue, such as having the units of grams, kilograms, and the like.Further, the recitations of numerical ranges by endpoints include theendpoints and all numbers within that numerical range. For example, aconcentration ranging from 40 percent by weight to 60 percent by weightincludes concentrations of 40 percent by weight, 60 percent by weight,and all concentrations there between (e.g., 40.1 percent, 41 percent, 45percent, 50 percent, 52.5 percent, 55 percent, 59 percent, etc.). Forexample, a concentration ranging from 40 phr to 60 phr includesconcentrations of 40 phr, 60 phr, and all concentrations there between(e.g., 40.1 phr, 41 phr, 45 phr, 50 phr, 52.5 phr, 55 phr, 59 phr,etc.).

Additional details are provided for the polymeric hydrogel component ofthe composition and/or elastomeric material. The composition and/orelastomeric material includes the polymeric hydrogel distributedthroughout the rubber, (i.e., the uncured rubber or the cured rubber)portion of the composition, and/or elastomeric material. Upon curing ofthe elastomeric material, at least a portion of the polymeric hydrogelin the composition may be entrapped (e.g., physically entrapped and/orchemically entrapped) by the cured rubber. For example, a portion of thepolymeric hydrogel can optionally be covalently bonded to the curedrubber in the elastomeric material, and/or substantially all of thepolymeric hydrogel in the elastomeric material can be physicallyentrapped by the cured rubber.

The polymeric hydrogel can be a thermoset hydrogel or a thermoplastichydrogel. The polymeric hydrogel can be an elastomeric hydrogel,including an elastomeric thermoset hydrogel or an elastomericthermoplastic hydrogel. The polymeric hydrogel can comprise one or morepolymers. The polymer can be selected from: polyurethanes (includingelastomeric polyurethanes, thermoplastic polyurethanes (TPUs), andelastomeric TPUs), polyesters, polyethers, polyamides, vinyl polymers(e.g., copolymers of vinyl alcohol, vinyl esters, ethylene, acrylates,methacrylates, styrene, and so on), polyacrylonitriles, polyphenyleneethers, polycarbonates, polyureas, polystyrenes, co-polymers thereof(including polyester-polyurethanes, polyether-polyurethanes,polycarbonate-polyurethanes, polyether block polyamides (PEBAs), andstyrene block copolymers), and any combination thereof, as describedherein. The polymer can include one or more polymers selected from thegroup consisting of polyesters, polyethers, polyamides, polyurethanes,polyolefins copolymers of each, and combinations thereof.

The polymeric hydrogel can comprise a single type of polymeric hydrogel,or a mixture of two or more types of polymeric hydrogels. The polymerichydrogel can comprise or consist essentially of a polyurethane hydrogel.The polymeric network of the elastomeric material can include one ormore polyurethane hydrogels. Polyurethane hydrogels are prepared fromone or more diisocyanate and one or more hydrophilic diol. A hydrophobicdiol can be used in addition to the hydrophilic diol. The polymerizationis normally carried out using roughly an equivalent amount of the dioland diisocyanate. Examples of hydrophilic diols are polyethylene glycolsor copolymers of ethylene glycol and propylene glycol. The diisocyanatecan be selected from a wide variety of aliphatic or aromaticdiisocyanates. The relative hydrophobicity of the resulting polymer isdetermined by the amount and type of the hydrophilic diols, the type andamount of the hydrophobic diols, and the type and amount of thediisocyanates.

The polymeric hydrogel can comprise or consist essentially of a polyureahydrogel. The polymeric network of the elastomeric material can includeone or more polyurea hydrogels. Polyurea hydrogels are prepared from oneor more diisocyanate and one or more hydrophilic diamine. A hydrophobicdiamine can be used in addition to the hydrophilic diamine. Thepolymerization is normally carried out using roughly an equivalentamount of the diamine and diisocyanate. Typical hydrophilic diamines areamine-terminated polyethylene oxides and amine-terminated copolymers ofpolyethylene oxide/polypropylene. Examples are JEFFAMINE diamines soldby Huntsman (The Woodlands, Tex., USA). The diisocyanate can be selectedfrom a wide variety of aliphatic or aromatic diisocyanates. Thehydrophobicity of the resulting polymer is determined by the amount andtype of the hydrophilic diamine, the type and amount of the hydrophobicamine, and the type and amount of the diisocyanate.

The polymeric hydrogel can comprise or consist essentially of apolyester hydrogel. The polymeric network of the elastomeric materialcan comprise one or more polyester hydrogels. Polyester hydrogels can beprepared from dicarboxylic acids (or dicarboxylic acid derivatives) anddiols where part or all of the diol is a hydrophilic diol. Examples ofhydrophilic diols are polyethylene glycols or copolymers of ethyleneglycol and propylene glycol. A second hydrophobic diol can also be usedto control the polarity of the final polymer. One or more diacid can beused which can be either aromatic or aliphatic. Block polyestersprepared from hydrophilic diols and lactones of hydroxyacids can also beused. The lactone can be polymerized on each end of the hydrophilic diolto produce a triblock polymer. In addition, these triblock segments canbe linked together to produce a multiblock polymer by reaction with adicarboxylic acid.

The polymeric hydrogel can comprise or consist essentially of apolycarbonate hydrogel. The polymeric network of the elastomericmaterial can comprise one or more polycarbonate hydrogels.Polycarbonates are typically prepared by reacting a diol with phosgeneor a carbonate diester. A hydrophilic polycarbonate is produced whenpart or all of the diol is a hydrophilic diol. Examples of hydrophilicdiols are hydroxyl terminated polyethers of ethylene glycol orpolyethers of ethylene glycol with propylene glycol. A secondhydrophobic diol can also be included to control the polarity of thefinal polymer.

The polymeric hydrogel can comprise or consist essentially of apolyetheramide hydrogel. The polymeric network of the elastomericmaterial can comprise one or more polyetheramide hydrogels.Polyetheramides are prepared from dicarboxylic acids (or dicarboxylicacid derivatives) and polyether diamines (a polyether terminated on eachend with an amino group). Hydrophilic amine-terminated polyethers can beused to produce hydrophilic polymers that can swell with water.Hydrophobic diamines can be used in conjunction with hydrophilicdiamines to control the hydrophilicity of the final polyetheramidehydrogel. In addition, the type dicarboxylic acid segment can beselected to control the polarity of the polyetheramide hydrogel and thephysical properties of the polyetheramide hydrogel. Typical hydrophilicdiamines are amine-terminated polyethylene oxides and amine-terminatedcopolymers of polyethylene oxide/polypropylene. Examples are JEFFAMINEdiamines sold by Huntsman (The Woodlands, Tex., USA).

The polymeric hydrogel can comprise or consist essentially of a hydrogelformed of addition polymers of ethylenically unsaturated monomers. Thepolymeric network of the elastomeric material can comprise one or morehydrogels formed of addition polymers of ethylenically unsaturatedmonomers. The addition polymers of ethylenically unsaturated monomerscan be random polymers. The addition polymers can be prepared by freeradical polymerization of one of more hydrophilic ethylenicallyunsaturated monomer and one or more hydrophobic ethylenicallyunsaturated monomers. Examples of hydrophilic monomers are acrylic acid,methacrylic acid, 2-acrylamido-2-methylpropane sulphonic acid, vinylsulphonic acid, sodium p-styrene sulfonate, [3-(methacryloylamino)propyl]trimethylammonium chloride, 2-hydroxyethyl methacrylate,acrylamide, N,N-dimethylacrylamide, 2-vinylpyrrolidone, (meth)acrylateesters of polyethylene glycol, and (meth)acrylate esters of polyethyleneglycol monomethyl ether. Examples of hydrophobic monomers are(meth)acrylate esters of C1 to C4 alcohols, polystyrene, polystyrenemethacrylate macromonomer and mono(meth)acrylate esters of siloxanes.The water uptake and physical characteristics of the resulting polymerichydrogel can be tuned by selection of the monomer and the amounts ofeach monomer type.

The addition polymers of ethylenically unsaturated monomers can be combpolymers. Comb polymers are produced when one of the monomers is amacromer (an oligomer with an ethylenically unsaturated group one end).In one case the main chain is hydrophilic while the side chains arehydrophobic. Alternatively the comb backbone can be hydrophobic whilethe side chains are hydrophilic. An example is a backbone of ahydrophobic monomer such as styrene with the methacrylate monoester ofpolyethylene glycol.

The addition polymers of ethylenically unsaturated monomers can be blockpolymers. Block polymers of ethylenically unsaturated monomers can beprepared by methods such as anionic polymerization or controlled freeradical polymerization. In one example, hydrogels are produced when thepolymer has both hydrophilic blocks and hydrophobic blocks. Thepolymeric hydrogel can be a diblock polymer (A-B) polymer, triblockpolymer (A-B-A) or multiblock polymer. Triblock polymers withhydrophobic end blocks and a hydrophilic center block can be useful forthis application. Block polymers can be prepared by other means as well.Partial hydrolysis of polyacrylonitrile polymers produces multiblockpolymers with hydrophilic domains (hydrolyzed) separated by hydrophobicdomains (unhydrolyzed) such that the partially hydrolyzed polymer actsas a hydrogel. The hydrolysis converts acrylonitrile units tohydrophilic acrylamide or acrylic acid units in a multiblock pattern.

The polymeric hydrogel can comprise or consist essentially of a hydrogelformed of copolymers. The polymeric network of the elastomeric materialcan comprise one or more hydrogels formed of copolymers. Copolymerscombine two or more types of monomeric units within each polymer chainto achieve the desired set of properties. Of particular interest arepolyurethane/polyurea copolymers, polyurethane/polyester copolymers, andpolyester/polycarbonate copolymers.

The polymeric hydrogel present may be characterized as including aplurality of polymer or copolymer chains in which each chain isindependently selected to comprise a combination of both hard segmentsand soft segments. These hard and soft segments can exist as phaseseparated regions within the polymeric network while the polymerichydrogel is in a solid (non-molten) state. The hard segments can formportions of the polymer chain backbones, and can exhibit highpolarities, allowing the hard segments of multiple polymer chains toaggregate together, or interact with each other, to formsemi-crystalline regions in the polymeric network. Typically, inpolymeric hydrogels having both soft segments and hard segments, each ofthe soft segments of the polymeric hydrogel independently has a greaterlevel of hydrophilicity than each of the hard segments.

A “semi-crystalline” or “crystalline” region has an ordered molecularstructure with sharp melting points, which remains solid until a givenquantity of heat is absorbed and then rapidly changes into a lowviscosity liquid. A “pseudo-crystalline” region has properties of acrystal, but does not exhibit a true crystalline diffraction pattern.For ease of reference, the term “crystalline region” is used herein tocollectively refer to a crystalline region, a semi-crystalline region,and a pseudo-crystalline region of a network of polymeric hydrogelchains. In some examples, the hard segments of polymeric hydrogels formcrystalline regions.

In comparison, the soft segments of these polymeric hydrogels can belonger, more flexible, hydrophilic regions and can form networks thatallow the elastomeric material to expand and swell under the pressure oftaken up water. The soft segments can constitute amorphous hydrophilicregions of the hydrogel, or of crosslinked portions of the elastomericmaterial. The soft segments, or amorphous regions, can also formportions of the backbones of the polymer chains of the polymerichydrogel along with the hard segments. Additionally, one or moreportions of the soft segments, or amorphous regions, can be grafted orotherwise represent pendant chains that extend from the backbones at thesoft segments. Each of the soft segments independently can include aplurality of hydroxyl groups, one or more poly(ethylene oxide) (PEO)segments, or both. The soft segments, or amorphous regions, can becovalently bonded to the hard segments, or crystalline regions (e.g.,through carbamate linkages). For example, the polymeric hydrogel caninclude a plurality of amorphous hydrophilic regions covalently bondedto the crystalline regions of the hard segments.

The polymeric hydrogel, or the polymeric network of the elastomericmaterial, or both, can include a plurality of polymer or copolymerchains having at least a portion of the chains comprising a hard segmentthat is physically crosslinked to other hard segments and a soft segmentcovalently bonded to the hard segment, such as through a carbamate groupor an ester group, among other functional groups.

The polymeric hydrogel or the polymeric network of the elastomericmaterial, or both, thereof may include a plurality of polymer orcopolymer chains. At least a portion of the polymer or copolymer chainscan include a first segment that forms at least a crystalline regionwith other hard segments of the copolymer chains and a second segment,such as a soft segment (e.g., a segment having polyether chains or oneor more ether groups) covalently bonded to the first segment. In thisexample, the soft segment forms amorphous regions of the hydrogel orcrosslinked polymeric network. The hydrogel or crosslinked polymericnetwork can include a plurality of polymer or copolymer chains, where atleast a portion of the polymer or copolymer chains has hydrophilicsegments.

The polymeric hydrogel can be an aliphatic polyurethane (TPU) resin thatcomprises a combination of hard segments and soft segments, wherein thehard segments include one or more segments having isocyanate groups. Thehard segments may include segments formed from hexamethylenediisocyanate (HDI) or 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI) incombination with 1,4-butanediol (1,4-BD) as a chain extender as shown informula (F-1A) (FIG. 14). The segments having isocyanate groups includesegments having isocyanate groups that are directly bonded to segmentsformed from the 1,4-BD. The soft segments may be formed frompoly(ethylene oxide) (PEO) as shown in formula (F-1B). The reactionproduct or polymeric hydrogel formed of both hard segments, HS, and thesoft segments, SS, may correspond to the formula shown in (F-1C),wherein the SS and HS correspond to the formulas shown in (F-1D) and(F-1E), respectively. The polymeric hydrogel may exhibit an averageratio of a number of soft segments to a number of hard segments (SS:HS)present in the copolymer chains of the polymeric hydrogel in the rangeof about 6:1 to about 100:1; alternatively, in the range of about 15:1to about 99:1; alternatively, in the range of about 30:1 to about 95:1;alternatively, in the range of about 50:1 to about 90:1; alternativelyin the range of 75:1 to 85:1. As the SS:HS ratio of the copolymerincreases, more PEO is present in the structure of the resin. While notwishing to be bound by theory, it is believed that the higher the SS:HSratio, the higher water uptake capacity is for the copolymer and fasterthe release kinetics associated therewith. A chemical description offormulas F-1A to F-1E is provided below.

As used herein, the term “polymer” refers to a chemical compound formedof a plurality of repeating structural units referred to as monomers.Polymers often are formed by a polymerization reaction in which theplurality of structural units become covalently bonded together. Whenthe monomer units forming the polymer all have the same chemicalstructure, the polymer is a homopolymer. When the polymer includes twoor more monomer units having different chemical structures, the polymeris a copolymer. One example of a type of copolymer is a terpolymer,which includes three different types of monomer units. The co-polymercan include two or more different monomers randomly distributed in thepolymer (e.g., a random co-polymer). Alternatively, one or more blockscontaining a plurality of a first type of monomer can be bonded to oneor more blocks containing a plurality of a second type of monomer,forming a block copolymer. A single monomer unit can include one or moredifferent chemical functional groups.

Polymers having repeating units which include two or more types ofchemical functional groups can be referred to as having two or moresegments. For example, a polymer having repeating units of the samechemical structure can be referred to as having repeating segments.Segments are commonly described as being relatively harder or softerbased on their chemical structures, and it is common for polymers toinclude relatively harder segments and relatively softer segments bondedto each other in a single monomeric unit or in different monomericunits. When the polymer includes repeating segments, physicalinteractions or chemical bonds can be present within the segments orbetween the segments or both within and between the segments. Examplesof segments often referred to as hard segments include segmentsincluding a urethane linkage, which can be formed from reacting anisocyanate with a polyol to form a polyurethane. Examples of segmentsoften referred to as soft segments include segments including an alkoxyfunctional group, such as segments including ether or ester functionalgroups, and polyester segments. Segments can be referred to based on thename of the functional group present in the segment (e.g., a polyethersegment, a polyester segment), as well as based on the name of thechemical structure which was reacted in order to form the segment (e.g.,a polyol-derived segment, an isocyanate-derived segment). When referringto segments of a particular functional group or of a particular chemicalstructure from which the segment was derived, it is understood that thepolymer can contain up to 10 mole percent of segments of otherfunctional groups or derived from other chemical structures. Forexample, as used herein, a polyether segment is understood to include upto 10 mole percent of non-polyether segments.

The composition of the present disclosure can be or can comprise athermoplastic material. The article comprising the elastomeric materialof the present disclosure can further comprise a thermoplastic material.The polymeric hydrogel of the composition and/or the elastomericmaterial can be a thermoplastic material. The composition can compriseat least one thermoplastic material in addition to the polymerichydrogel. In general, a thermoplastic material softens or melts whenheated and returns to a solid state when cooled. The thermoplasticmaterial transitions from a solid state to a softened state when itstemperature is increased to a temperature at or above its softeningtemperature, and a liquid state when its temperature is increased to atemperature at or above its melting temperature. When sufficientlycooled, the thermoplastic material transitions from the softened orliquid state to the solid state. As such, the thermoplastic material maybe softened or melted, molded, cooled, re-softened or re-melted,re-molded, and cooled again through multiple cycles. For amorphousthermoplastic polymers, the solid state is understood to be the“rubbery” state above the glass transition temperature of the polymer.The thermoplastic material can have a melting temperature from about 90degrees C. to about 190 degrees C. when determined in accordance withASTM D3418-97 as described herein below, and includes all subrangestherein in increments of 1 degree. The thermoplastic material can have amelting temperature from about 93 degrees C. to about 99 degrees C. whendetermined in accordance with ASTM D3418-97 as described herein below.The thermoplastic material can have a melting temperature from about 112degrees C. to about 118 degrees C. when determined in accordance withASTM D3418-97 as described herein below.

The glass transition temperature is the temperature at which anamorphous polymer transitions from a relatively brittle “glassy” stateto a relatively more flexible “rubbery” state. The thermoplasticmaterial can have a glass transition temperature from about −20 degreesC. to about 30 degrees C. when determined in accordance with ASTMD3418-97 as described herein below. The thermoplastic material can havea glass transition temperature (from about −13 degree C. to about −7degrees C. when determined in accordance with ASTM D3418-97 as describedherein below. The thermoplastic material can have a glass transitiontemperature from about 17 degrees C. to about 23 degrees C. whendetermined in accordance with ASTM D3418-97 as described herein below.

The thermoplastic material can have a melt flow index from about 10 toabout 30 cubic centimeters per 10 minutes (cm³/10 min) when tested inaccordance with ASTM D1238-13 as described herein below at 160 degreesC. using a weight of 2.16 kilograms (kg). The thermoplastic material canhave a melt flow index from about 22 cm³/10 min to about 28 cm³/10 minwhen tested in accordance with ASTM D1238-13 as described herein belowat 160 degrees C. using a weight of 2.16 kg.

The elastomeric material can have a cold Ross flex test result of about120,000 to about 180,000 cycles without cracking or whitening whentested on a plaque of the elastomeric material in accordance with thecold Ross flex test as described herein below. The elastomeric materialcan have a cold Ross flex test result of about 140,000 to about 160,000cycles without cracking or whitening when tested on a plaque of theelastomeric material in accordance with the cold Ross flex test asdescribed herein below.

The elastomeric material can have a modulus from about 5 megaPascals(MPa) to about 100 MPa when determined on a plaque in accordance withASTM D412-98 Standard Test Methods for Vulcanized Rubber andThermoplastic Rubbers and Thermoplastic Elastomers-Tension withmodifications described herein below. The elastomeric material can havea modulus from about 20 MPa to about 80 MPa when determined on a plaquein accordance with ASTM D412-98 Standard Test Methods for VulcanizedRubber and Thermoplastic Rubbers and Thermoplastic Elastomers-Tensionwith modifications described herein below.

The elastomeric material is a thermoset material. A “thermoset material”is understood to refer to a material which cannot be heated and melted,as its melting temperature is at or above its decomposition temperature.A “thermoset material” refers to a composition which comprises at leastone thermoset polymer. The thermoset polymer and/or thermoset materialcan be prepared from a precursor (e.g., an uncured or partially curedpolymer or material) using actinic radiation (e.g., thermal energy,ultraviolet radiation, visible radiation, high energy radiation,infrared radiation) to form a partially cured or fully cured polymer ormaterial which no longer remains fully thermoplastic. In some cases, thecured or partially cured elastomeric material may retain somethermoplastic properties, in that it is possible to partially soften andmold the elastomeric material at elevated temperatures and/or pressures,but it is not possible to melt the elastomeric material. The curing canbe promoted, for example, with the use of high pressure and/or acatalyst. The curing process is irreversible since it results incrosslinking and/or polymerization reactions of the precursors. Theuncured compositions or partially cured elastomeric materials can bemalleable or liquid prior to curing. In some cases, the uncuredcomposition or partially cured elastomeric materials can be molded intotheir final shape, or used as adhesives. Once hardened, a thermosetmaterial cannot be re-melted in order to be reshaped, but it may bepossible to soften it. The textured surface can be formed by partiallyor fully curing the composition to lock in the textured surface into theelastomeric material.

The composition and/or the elastomeric material can comprise apolyurethane. The article comprising the elastomeric material canfurther include one or more components comprising a polyurethane. Thepolyurethane can be a thermoplastic polyurethane (also referred to as“TPU”). Alternatively, the polyurethane can be a thermoset polyurethane.Additionally, the polyurethane can be an elastomeric polyurethane,including an elastomeric TPU or an elastomeric thermoset polyurethane.The elastomeric polyurethane can include hard and soft segments. Thehard segments can comprise or consist of urethane segments (e.g.,isocyanate-derived segments). The soft segments can comprise or consistof alkoxy segments (e.g., polyol-derived segments including polyethersegments, or polyester segments, or a combination of polyether segmentsand polyester segments). The polyurethane can comprise or consistessentially of an elastomeric polyurethane having repeating hardsegments and repeating soft segments.

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce polymer chainshaving carbamate linkages (—N(CO)O—) as illustrated below in Formula 1,where the isocyanate(s) each preferably include two or more isocyanate(—NCO) groups per molecule, such as 2, 3, or 4 isocyanate groups permolecule (although, mono-functional isocyanates can also be optionallyincluded, e.g., as chain terminating units).

Each R₁ group and R₂ group independently is an aliphatic or aromaticgroup. Optionally, each R₂ can be a relatively hydrophilic group,including a group having one or more hydroxyl groups.

Additionally, the isocyanates can also be chain extended with one ormore chain extenders to bridge two or more isocyanates, increasing thelength of the hard segment. This can produce polyurethane polymer chainsas illustrated below in Formula 2, where R₃ includes the chain extender.As with each R₁ and R₂, each R₃ independently is an aliphatic oraromatic functional group.

Each R₁ group in Formulas 1 and 2 can independently include a linear orbranched group having from 3 to 30 carbon atoms, based on the particularisocyanate(s) used, and can be aliphatic, aromatic, or include acombination of aliphatic portions(s) and aromatic portion(s). The term“aliphatic” refers to a saturated or unsaturated organic molecule orportion of a molecule that does not include a cyclically conjugated ringsystem having delocalized pi electrons. In comparison, the term“aromatic” refers to an organic molecule or portion of a molecule havinga cyclically conjugated ring system with delocalized pi electrons, whichexhibits greater stability than a hypothetical ring system havinglocalized pi electrons.

Each R₁ group can be present in an amount of about 5 percent to about 85percent by weight, from about 5 percent to about 70 percent by weight,or from about 10 percent to about 50 percent by weight, based on thetotal weight of the reactant compounds or monomers which form thepolymer.

In aliphatic embodiments (from aliphatic isocyanate(s)), each R₁ groupcan include a linear aliphatic group, a branched aliphatic group, acycloaliphatic group, or combinations thereof. For instance, each R₁group can include a linear or branched alkylene group having from 3 to20 carbon atoms (e.g., an alkylene having from 4 to 15 carbon atoms, oran alkylene having from 6 to 10 carbon atoms), one or more cycloalkylenegroups having from 3 to 8 carbon atoms (e.g., cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl), and combinationsthereof. The term “alkene” or “alkylene” as used herein refers to abivalent hydrocarbon. When used in association with the term C_(n) itmeans the alkene or alkylene group has “n” carbon atoms. For example,01-6 alkylene refers to an alkylene group having, e.g., 1, 2, 3, 4, 5,or 6 carbon atoms.

Examples of suitable aliphatic diisocyanates for producing thepolyurethane polymer chains include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI), butylenediisocyanate (BDI),bisisocyanatocyclohexylmethane (HMDI), 2,2,4-trimethylhexamethylenediisocyanate (TMDI), bisisocyanatomethylcyclohexane,bisisocyanatomethyltricyclodecane, norbornane diisocyanate (NDI),cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate(H12MDI), diisocyanatododecane, lysine diisocyanate, and combinationsthereof.

The isocyanate-derived segments can include segments derived fromaliphatic diisocyanate. A majority of the isocyanate-derived segmentscan comprise segments derived from aliphatic diisocyanates. At least 90percent of the isocyanate-derived segments are derived from aliphaticdiisocyanates. The isocyanate-derived segments can consist essentiallyof segments derived from aliphatic diisocyanates. The aliphaticdiisocyanate-derived segments can be derived substantially (e.g., about50 percent or more, about 60 percent or more, about 70 percent or more,about 80 percent or more, about 90 percent or more) from linearaliphatic diisocyanates. At least 80 percent of the aliphaticdiisocyanate-derived segments can be derived from aliphaticdiisocyanates that are free of side chains. The segments derived fromaliphatic diisocyanates can include linear aliphatic diisocyanateshaving from 2 to 10 carbon atoms.

When the isocyanate-derived segments are derived from aromaticisocyanate(s)), each R₁ group can include one or more aromatic groups,such as phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unlessotherwise indicated, an aromatic group can be an unsubstituted aromaticgroup or a substituted aromatic group, and can also includeheteroaromatic groups. “Heteroaromatic” refers to monocyclic orpolycyclic (e.g., fused bicyclic and fused tricyclic) aromatic ringsystems, where one to four ring atoms are selected from oxygen,nitrogen, or sulfur, and the remaining ring atoms are carbon, and wherethe ring system is joined to the remainder of the molecule by any of thering atoms. Examples of suitable heteroaryl groups include pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzoxazolyl, benzimidazolyl, andbenzothiazolyl groups.

Examples of suitable aromatic diisocyanates for producing thepolyurethane polymer chains include toluene diisocyanate (TDI), TDIadducts with trimethyloylpropane (TMP), methylene diphenyl diisocyanate(MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate(TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene1,5-diisocyanate (NDI), 1,5-tetrahydronaphthalene diisocyanate,para-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), 4,4′-dibenzyl diisocyanate (DBDI),4-chloro-1,3-phenylene diisocyanate, and combinations thereof. Thepolymer chains can be substantially free of aromatic groups.

The polyurethane polymer chains can be produced from diisocyanatesincluding HMDI, TDI, MDI, H₁₂ aliphatics, and combinations thereof. Forexample, the polyurethane can comprise one or more polyurethane polymerchains produced from diisocyanates including HMDI, TDI, MDI, H₁₂aliphatics, and combinations thereof.

Polyurethane chains which are at least partially crosslinked or whichcan be crosslinked, can be used in accordance with the presentdisclosure. It is possible to produce crosslinked or crosslinkablepolyurethane chains by reacting multi-functional isocyanates to form thepolyurethane. Examples of suitable triisocyanates for producing thepolyurethane chains include TDI, HDI, and IPDI adducts withtrimethyloylpropane (TMP), uretdiones (i.e., dimerized isocyanates),polymeric MDI, and combinations thereof.

The R₃ group in Formula 2 can include a linear or branched group havingfrom 2 to 10 carbon atoms, based on the particular chain extender polyolused, and can be, for example, aliphatic, aromatic, or an ether orpolyether. Examples of suitable chain extender polyols for producing thepolyurethane include ethylene glycol, lower oligomers of ethylene glycol(e.g., diethylene glycol, triethylene glycol, and tetraethylene glycol),1,2-propylene glycol, 1,3-propylene glycol, lower oligomers of propyleneglycol (e.g., dipropylene glycol, tripropylene glycol, andtetrapropylene glycol), 1,4-butylene glycol, 2,3-butylene glycol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 2-ethyl-1,6-hexanediol,1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, dihydroxyalkylatedaromatic compounds (e.g., bis(2-hydroxyethyl) ethers of hydroquinone andresorcinol, xylene-a,a-diols, bis(2-hydroxyethyl) ethers ofxylene-a,a-diols, and combinations thereof.

The R₂ group in Formula 1 and 2 can include a polyether group, apolyester group, a polycarbonate group, an aliphatic group, or anaromatic group. Each R₂ group can be present in an amount of about 5percent to about 85 percent by weight, from about 5 percent to about 70percent by weight, or from about 10 percent to about 50 percent byweight, based on the total weight of the reactant monomers.

At least one R₂ group of the polyurethane includes a polyether segment(i.e., a segment having one or more ether groups). Suitable polyethergroups include, but are not limited to, polyethylene oxide (PEO),polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof. The term“alkyl” as used herein refers to straight chained and branched saturatedhydrocarbon groups containing one to thirty carbon atoms, for example,one to twenty carbon atoms, or one to ten carbon atoms. When used inassociation with the term C_(n) it means the alkyl group has “n” carbonatoms. For example, C₄ alkyl refers to an alkyl group that has 4 carbonatoms. C₁₋₇ alkyl refers to an alkyl group having a number of carbonatoms encompassing the entire range (i.e., 1 to 7 carbon atoms), as wellas all subgroups (e.g., 1-6, 2-7, 1-5, 3-6, 1, 2, 3, 4, 5, 6, and 7carbon atoms). Non-limiting examples of alkyl groups include, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl(1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unlessotherwise indicated, an alkyl group can be an unsubstituted alkyl groupor a substituted alkyl group.

In some examples of the polyurethane, the at least one R₂ group includesa polyester group. The polyester group can be derived from thepolyesterification of one or more dihydric alcohols (e.g., ethyleneglycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol,1,3-butanediol, 2-methylpentanediol, 1,5,diethylene glycol,1,5-pentanediol, 1,5-hexanediol, 1,2-dodecanediol,cyclohexanedimethanol, and combinations thereof) with one or moredicarboxylic acids (e.g., adipic acid, succinic acid, sebacic acid,suberic acid, methyladipic acid, glutaric acid, pimelic acid, azelaicacid, thiodipropionic acid and citraconic acid and combinationsthereof). The polyester group also can be derived from polycarbonateprepolymers, such as poly(hexamethylene carbonate) glycol,poly(propylene carbonate) glycol, poly(tetramethylene carbonate)glycol,and poly(nonanemethylene carbonate) glycol. Suitable polyesters caninclude, for example, polyethylene adipate (PEA), poly(1,4-butyleneadipate), poly(tetramethylene adipate), poly(hexamethylene adipate),polycaprolactone, polyhexamethylene carbonate, poly(propylenecarbonate), poly(tetramethylene carbonate), poly(nonanemethylenecarbonate), and combinations thereof.

At least one R₂ group can include a polycarbonate group. Thepolycarbonate group can be derived from the reaction of one or moredihydric alcohols (e.g., ethylene glycol, 1,3-propylene glycol,1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol,2-methylpentanediol, 1,5, diethylene glycol, 1,5-pentanediol,1,5-hexanediol, 1,2-dodecanediol, cyclohexanedimethanol, andcombinations thereof) with ethylene carbonate.

The aliphatic group can be linear and can include, for example, analkylene chain having from 1 to 20 carbon atoms or an alkenylene chainhaving from 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene,butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, ethenylene, propenylene,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene). Theterm “alkene” or “alkylene” refers to a bivalent hydrocarbon. The term“alkenylene” refers to a bivalent hydrocarbon molecule or portion of amolecule having at least one double bond.

The aliphatic and aromatic groups can be substituted with one or morependant relatively hydrophilic and/or charged groups. The pendanthydrophilic group can include one or more (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10 or more) hydroxyl groups. The pendant hydrophilic group includes oneor more (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10 or more) amino groups. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) carboxylate groups. For example, thealiphatic group can include one or more polyacrylic acid group. In somecases, the pendant hydrophilic group includes one or more (e.g., 2, 3,4, 5, 6, 7, 8, 9, 10 or more) sulfonate groups. In some cases, thependant hydrophilic group includes one or more (e.g., 2, 3, 4, 5, 6, 7,8, 9, 10 or more) phosphate groups. In some examples, the pendanthydrophilic group includes one or more ammonium groups (e.g., tertiaryand/or quaternary ammonium). In other examples, the pendant hydrophilicgroup includes one or more zwitterionic groups (e.g., a betaine, such aspoly(carboxybetaine (pCB) and ammonium phosphonate groups such as aphosphatidylcholine group).

The R₂ group can include charged groups that are capable of binding to acounterion to ionically crosslink the polymer and form ionomers. Forexample, R₂ is an aliphatic or aromatic group having pendant amino,carboxylate, sulfonate, phosphate, ammonium, or zwitterionic groups, orcombinations thereof.

When a pendant hydrophilic group is present, the pendant hydrophilicgroup can be at least one polyether group, such as two polyether groups.In other cases, the pendant hydrophilic group is at least one polyester.The pendant hydrophilic group can be a polylactone group (e.g.,polyvinylpyrrolidone). Each carbon atom of the pendant hydrophilic groupcan optionally be substituted with, e.g., an alkyl group having from 1to 6 carbon atoms. The aliphatic and aromatic groups can be graftpolymeric groups, wherein the pendant groups are homopolymeric groups(e.g., polyether groups, polyester groups, polyvinylpyrrolidone groups).

The pendant hydrophilic group can be a polyether group (e.g., apolyethylene oxide (PEO) group, a polyethylene glycol (PEG) group), apolyvinylpyrrolidone group, a polyacrylic acid group, or combinationsthereof.

The pendant hydrophilic group can be bonded to the aliphatic group oraromatic group through a linker. The linker can be any bifunctionalsmall molecule (e.g., one having from 1 to 20 carbon atoms) capable oflinking the pendant hydrophilic group to the aliphatic or aromaticgroup. For example, the linker can include a diisocyanate group, aspreviously described herein, which when linked to the pendanthydrophilic group and to the aliphatic or aromatic group forms acarbamate bond. The linker can be 4,4′-diphenylmethane diisocyanate(MDI), as shown below.

The pendant hydrophilic group can be a polyethylene oxide group and thelinking group can be MDI, as shown below.

The pendant hydrophilic group can be functionalized to enable it to bondto the aliphatic or aromatic group, optionally through the linker. Forexample, when the pendant hydrophilic group includes an alkene group,which can undergo a Michael addition with a sulfhydryl-containingbifunctional molecule (i.e., a molecule having a second reactive group,such as a hydroxyl group or amino group), resulting in a hydrophilicgroup that can react with the polymer backbone, optionally through thelinker, using the second reactive group. For example, when the pendanthydrophilic group is a polyvinylpyrrolidone group, it can react with thesulfhydryl group on mercaptoethanol to result in hydroxyl-functionalizedpolyvinylpyrrolidone, as shown below.

At least one R₂ group in the polyurethane can include apolytetramethylene oxide group. At least one R₂ group of thepolyurethane can include an aliphatic polyol group functionalized with apolyethylene oxide group or polyvinylpyrrolidone group, such as thepolyols described in E.P. Patent No. 2 462 908, which is herebyincorporated by reference. For example, the R₂ group can be derived fromthe reaction product of a polyol (e.g., pentaerythritol or2,2,3-trihydroxypropanol) and either MDI-derivatized methoxypolyethyleneglycol (to obtain compounds as shown in Formulas 6 or 7) or withMDI-derivatized polyvinylpyrrolidone (to obtain compounds as shown inFormulas 8 or 9) that had been previously been reacted withmercaptoethanol, as shown below.

At least one R₂ of the polyurethane can be a polysiloxane, In thesecases, the R₂ group can be derived from a silicone monomer of Formula10, such as a silicone monomer disclosed in U.S. Pat. No. 5,969,076,which is hereby incorporated by reference:

wherein: a is 1 to 10 or larger (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or10); each R₄ independently is hydrogen, an alkyl group having from 1 to18 carbon atoms, an alkenyl group having from 2 to 18 carbon atoms,aryl, or polyether; and each R₅ independently is an alkylene grouphaving from 1 to 10 carbon atoms, polyether, or polyurethane.

Each R₄ group can independently be a H, an alkyl group having from 1 to10 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, anaryl group having from 1 to 6 carbon atoms, polyethylene, polypropylene,or polybutylene group. Each R₄ group can independently be selected fromthe group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, s-butyl, t-butyl, ethenyl, propenyl, phenyl, and polyethylenegroups.

Each R₅ group can independently include an alkylene group having from 1to 10 carbon atoms (e.g., a methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, or decylene group).Each R₅ group can be a polyether group (e.g., a polyethylene,polypropylene, or polybutylene group). Each R₅ group can be apolyurethane group.

Optionally, the polyurethane can include an at least partiallycrosslinked polymeric network that includes polymer chains that arederivatives of polyurethane. The level of crosslinking can be such thatthe polyurethane retains thermoplastic properties (i.e., the crosslinkedthermoplastic polyurethane can be melted and re-solidified under theprocessing conditions described herein). The crosslinked polyurethanecan be a thermoset polymer. This crosslinked polymeric network can beproduced by polymerizing one or more isocyanates with one or morepolyamino compounds, polysulfhydryl compounds, or combinations thereof,as shown in Formulas 11 and 12, below:

where the variables are as described above. Additionally, theisocyanates can also be chain extended with one or more polyamino orpolythiol chain extenders to bridge two or more isocyanates, such aspreviously described for the polyurethanes of Formula 2.

The polyurethane chain can be physically crosslinked to anotherpolyurethane chain through e.g., nonpolar or polar interactions betweenthe urethane or carbamate groups of the polymers (the hard segments).The R₁ group in Formula 1, and the R₁ and R₃ groups in Formula 2, formthe portion of the polymer often referred to as the “hard segment”, andthe R₂ group forms the portion of the polymer often referred to as the“soft segment”. The soft segment is covalently bonded to the hardsegment. The polyurethane having physically crosslinked hard and softsegments can be a hydrophilic polyurethane (i.e., a polyurethane,including a thermoplastic polyurethane, including hydrophilic groups asdisclosed herein).

One or more of the polyurethanes can be produced by polymerizing one ormore isocyanates with one or more polyols to produce copolymer chainshaving carbamate linkages (—N(C═O)O—) and one or more water-uptakeenhancing moieties, where the polymer chain includes one or morewater-uptake enhancing moieties (e.g., a monomer in polymer chain). Thewater-uptake enhancing moiety can be added to the chain of Formula 1 or2 (e.g., within the chain and/or onto the chain as a side chain).Inclusion of the water-uptake enhancing moiety can enable the formationof a polyurethane hydrogel.

The polyurethane can include one or more water-uptake enhancingmoieties. The water-uptake enhancing moiety can have at least onehydrophilic (e.g., poly(ethylene oxide)), ionic or potentially ionicgroup.\ A polyurethane can be formed by incorporating a moiety bearingat least one hydrophilic group or a group that can be made hydrophilic(e.g., by chemical modifications such as neutralization) into thepolymer chain. For example, these compounds can be nonionic, anionic,cationic or zwitterionic or the combination thereof. In one example,anionic groups such as carboxylic acid groups can be incorporated intothe chain in an inactive form and subsequently activated by asalt-forming compound, such as a tertiary amine. Other water-uptakeenhancing moieties can also be reacted into the backbone throughurethane linkages or urea linkages, including lateral or terminalhydrophilic ethylene oxide or ureido units.

The water-uptake enhancing moiety can be a one that includes carboxylgroups.

Water-uptake enhancing moiety that include a carboxyl group can beformed from hydroxy-carboxylic acids having the general formula(HO)_(x)Q(COOH)_(y), where Q can be a straight or branched bivalenthydrocarbon radical containing 1 to 12 carbon atoms, and x and y caneach independently be 1 to 3. Illustrative examples includedimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), citricacid, tartaric acid, glycolic acid, lactic acid, malic acid,dihydroxymalic acid, dihydroxytartaric acid, and the like, and mixturesthereof.

The water-uptake enhancing moiety can include reactive polymeric polyolcomponents that contain pendant anionic groups that can be polymerizedinto the backbone to impart water dispersible characteristics to thepolyurethane. Anionic functional polymeric polyols can include anionicpolyester polyols, anionic polyether polyols, and anionic polycarbonatepolyols, where additional detail is provided in U.S. Pat. No. 5,334,690.

The water-uptake enhancing moiety can include a side chain hydrophilicmonomer. For example, the water-uptake enhancing moiety including theside chain hydrophilic monomer can include alkylene oxide polymers andcopolymers in which the alkylene oxide groups have from 2-10 carbonatoms as shown in U.S. Pat. No. 6,897,281. Additional types ofwater-uptake enhancing moieties can include thioglycolic acid,2,6-dihydroxybenzoic acid, sulfoisophthalic acid, polyethylene glycol,and the like, and mixtures thereof. Additional details regardingwater-dispersible enhancing moieties can be found in U.S. Pat. No.7,476,705.

Polyamides

The composition and/or the elastomeric material can comprise apolyamide. The article comprising the elastomeric material can furtherone or more components comprising a polyamide. The polyamide can be athermoplastic polyamide, or a thermoset polyamide. The polyamide can bean elastomeric polyamide, including an elastomeric thermoplasticpolyamide or an elastomeric thermoset polyamide. The polyamide can be apolyamide homopolymer having repeating polyamide segments of the samechemical structure. Alternatively, the polyamide can comprise a numberof polyamide segments having different polyamide chemical structures(e.g., polyamide 6 segments, polyamide 11 segments, polyamide 12segments, polyamide 66 segments, etc.). The polyamide segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

The polyamide can be a co-polyamide (i.e., a co-polymer includingpolyamide segments and non-polyamide segments). The polyamide segmentsof the co-polyamide can comprise or consist of polyamide 6 segments,polyamide 11 segments, polyamide 12 segments, polyamide 66 segments, orany combination thereof. The polyamide segments of the co-polyamide canbe arranged randomly, or can be arranged as repeating segments. Thepolyamide segments can comprise or consist of polyamide 6 segments, orpolyamide 12 segments, or both polyamide 6 segment and polyamide 12segments. In the example where the polyamide segments of theco-polyamide include of polyamide 6 segments and polyamide 12 segments,the segments can be arranged randomly. The non-polyamide segments of theco-polyamide can comprise or consist of polyether segments, polyestersegments, or both polyether segments and polyester segments. Theco-polyamide can be a block co-polyamide, or can be a randomco-polyamide. The copolyamide can be formed from the polycondensation ofa polyamide oligomer or prepolymer with a second oligomer prepolymer toform a copolyamide (i.e., a co-polymer including polyamide segments.Optionally, the second prepolymer can be a hydrophilic prepolymer.

The polyamide can be a polyamide-containing block co-polymer. Forexample, the block co-polymer can have repeating hard segments, andrepeating soft segments. The hard segments can comprise polyamidesegments, and the soft segments can comprise non-polyamide segments. Thepolyamide-containing block co-polymer can be an elastomeric co-polyamidecomprising or consisting of polyamide-containing block co-polymershaving repeating hard segments and repeating soft segments. In blockco-polymers, including block co-polymers having repeating hard segmentsand soft segments, physical crosslinks can be present within thesegments or between the segments or both within and between thesegments.

The polyamide itself, or the polyamide segment of thepolyamide-containing block co-polymer can be derived from thecondensation of polyamide prepolymers, such as lactams, amino acids,and/or diamino compounds with dicarboxylic acids, or activated formsthereof. The resulting polyamide segments include amide linkages(—(CO)NH—). The term “amino acid” refers to a molecule having at leastone amino group and at least one carboxyl group. Each polyamide segmentof the polyamide can be the same or different.

The polyamide or the polyamide segment of the polyamide-containing blockco-polymer can be derived from the polycondensation of lactams and/oramino acids, and can include an amide segment having a structure shownin Formula 13, below, wherein R₆ group represents the portion of thepolyamide derived from the lactam or amino acid.

The R₆ group can be derived from a lactam. The R₆ group can be derivedfrom a lactam group having from 3 to 20 carbon atoms, or a lactam grouphaving from 4 to 15 carbon atoms, or a lactam group having from 6 to 12carbon atoms. The R₆ group can be derived from caprolactam orlaurolactam. The R₆ group can be derived from one or more amino acids.The R₆ group can be derived from an amino acid group having from 4 to 25carbon atoms, or an amino acid group having from 5 to 20 carbon atoms,or an amino acid group having from 8 to 15 carbon atoms. The R₆ groupcan be derived from 12-aminolauric acid or 11-aminoundecanoic acid.

Optionally, in order to increase the relative degree of hydrophilicityof the polyamide-containing block co-polymer, Formula 13 can include apolyamide-polyether block copolymer segment, as shown below:

wherein m is 3-20, and n is 1-8. Optionally, m is 4-15, or 6-12 (e.g.,6, 7, 8, 9, 10, 11, or 12), and n is 1, 2, or 3. For example, m can be11 or 12, and n can be 1 or 3. The polyamide or the polyamide segment ofthe polyamide-containing block co-polymer can be derived from thecondensation of diamino compounds with dicarboxylic acids, or activatedforms thereof, and can include an amide segment having a structure shownin Formula 15, below, wherein the R₇ group represents the portion of thepolyamide derived from the diamino compound, and the R₈ group representsthe portion derived from the dicarboxylic acid compound:

The R₇ group can be derived from a diamino compound that includes analiphatic group having from 4 to 15 carbon atoms, or from 5 to 10 carbonatoms, or from 6 to 9 carbon atoms. The diamino compound can include anaromatic group, such as phenyl, naphthyl, xylyl, and tolyl. Suitablediamino compounds from which the R₇ group can be derived include, butare not limited to, hexamethylene diamine (HMD), tetramethylene diamine,trimethyl hexamethylene diamine (TMD),m-xylylene diamine (MXD), and1,5-pentamine diamine. The R₈ group can be derived from a dicarboxylicacid or activated form thereof, including an aliphatic group having from4 to 15 carbon atoms, or from 5 to 12 carbon atoms, or from 6 to 10carbon atoms. The dicarboxylic acid or activated form thereof from whichR₈ can be derived includes an aromatic group, such as phenyl, naphthyl,xylyl, and tolyl groups. Suitable carboxylic acids or activated formsthereof from which R₈ can be derived include adipic acid, sebacic acid,terephthalic acid, and isophthalic acid. The polyamide chain can besubstantially free of aromatic groups.

Each polyamide segment of the polyamide (including thepolyamide-containing block co-polymer) can be independently derived froma polyamide prepolymer selected from the group consisting of12-aminolauric acid, caprolactam, hexamethylene diamine and adipic acid.

The polyamide can comprise or consist essentially of apoly(ether-block-amide). The poly(ether-block-amide) can be formed fromthe polycondensation of a carboxylic acid terminated polyamideprepolymer and a hydroxyl terminated polyether prepolymer to form apoly(ether-block-amide), as shown in Formula 16:

The poly(ether block amide) polymer can be prepared by polycondensationof polyamide blocks containing reactive ends with polyether blockscontaining reactive ends. Examples include: 1) polyamide blockscontaining diamine chain ends with polyoxyalkylene blocks containingcarboxylic chain ends; 2) polyamide blocks containing dicarboxylic chainends with polyoxyalkylene blocks containing diamine chain ends obtainedby cyanoethylation and hydrogenation of aliphatic dihydroxylatedalpha-omega polyoxyalkylenes known as polyether diols; 3) polyamideblocks containing dicarboxylic chain ends with polyether diols, theproducts obtained in this particular case being polyetheresteramides.The polyamide block of the poly(ether-block-amide) can be derived fromlactams, amino acids, and/or diamino compounds with dicarboxylic acidsas previously described. The polyether block can be derived from one ormore polyethers selected from the group consisting of polyethylene oxide(PEO), polypropylene oxide (PPO), polytetrahydrofuran (PTHF),polytetramethylene oxide (PTMO), and combinations thereof.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks comprising dicarboxylic chain ends derived from thecondensation of α, ω-aminocarboxylic acids, of lactams or ofdicarboxylic acids and diamines in the presence of a chain-limitingdicarboxylic acid. In poly(ether block amide) polymers of this type, aα, ω-aminocarboxylic acid such as aminoundecanoic acid can be used; alactam such as caprolactam or lauryllactam can be used; a dicarboxylicacid such as adipic acid, decanedioic acid or dodecanedioic acid can beused; and a diamine such as hexamethylenediamine can be used; or variouscombinations of any of the foregoing. The copolymer can comprisepolyamide blocks comprising polyamide 12 or of polyamide 6.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of one or more a,w-aminocarboxylic acids and/or of one or more lactams containing from 6to 12 carbon atoms in the presence of a dicarboxylic acid containingfrom 4 to 12 carbon atoms, and are of low mass, i.e., they have anumber-average molecular weight of from 400 to 1000. In poly(ether blockamide) polymers of this type, an a, w-aminocarboxylic acid such asaminoundecanoic acid or aminododecanoic acid can be used; a dicarboxylicacid such as adipic acid, sebacic acid, isophthalic acid, butanedioicacid, 1,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium orlithium salt of sulphoisophthalic acid, dimerized fatty acids (thesedimerized fatty acids have a dimer content of at least 98 weight percentand are preferably hydrogenated) and dodecanedioic acidHOOC—(CH₂)₁₀—COOH can be used; and a lactam such as caprolactam andlauryllactam can be used; or various combinations of any of theforegoing. The copolymer can comprise polyamide blocks obtained bycondensation of lauryllactam in the presence of adipic acid ordodecanedioic acid and with a number average molecular weight of atleast 750 have a melting temperature of from about 127 to about 130degrees C. The various constituents of the polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., or from about 90 degrees C. to about 135 degrees C.

The poly(ether block amide) polymers can include those comprisingpolyamide blocks derived from the condensation of at least one a,w-aminocarboxylic acid (or a lactam), at least one diamine and at leastone dicarboxylic acid. In copolymers of this type, a α,ω-aminocarboxylicacid, the lactam and the dicarboxylic acid can be chosen from thosedescribed herein above and the diamine that can be used can include analiphatic diamine containing from 6 to 12 atoms and can be acyclicand/or saturated cyclic such as, but not limited to,hexamethylenediamine, piperazine, 1-aminoethylpiperazine,bisaminopropylpiperazine, tetramethylenediamine, octamethylene-diamine,decamethylenediamine, dodecamethylenediamine, 1,5-diaminohexane,2,2,4-trimethyl-1,6-diaminohexane, diamine polyols, isophoronediamine(IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane(BACM) and bis(3-methyl-4-aminocyclohexyl)methane (BMACM).

The polyamide can be a thermoplastic polyamide and the constituents ofthe polyamide block and their proportion can be chosen in order toobtain a melting temperature of less than 150 degrees C., such as amelting point of from about 90 degrees C. to about 135 degrees C. Thevarious constituents of the thermoplastic polyamide block and theirproportion can be chosen in order to obtain a melting point of less than150 degrees C., such as from about and 90 degrees C. to about 135degrees C.

The number average molar mass of the polyamide blocks can be from about300 grams per mole to about 15,000 grams per mole, from about 500 gramsper mole to about 10,000 grams per mole, from about 500 grams per moleto about 6,000 grams per mole, from about 500 grams per mole to about5,000 grams per mole, or from about 600 grams per mole to about 5,000grams per mole. The number average molecular weight of the polyetherblock can range from about 100 to about 6,000, from about 400 to about3000, or from about 200 to about 3,000. The polyether (PE) content (x)of the poly(ether block amide) polymer can be from about 0.05 to about0.8 (i.e., from about 5 mole percent to about 80 mole percent). Thepolyether blocks can be present in the polyamide in an amount of fromabout 10 weight percent to about 50 weight percent, from about 20 weightpercent to about 40 weight percent, or from about 30 weight percent toabout 40 weight percent. The polyamide blocks can be present in thepolyamide in an amount of from about 50 weight percent to about 90weight percent, from about 60 weight percent to about 80 weight percent,or from about 70 weight percent to about 90 weight percent.

The polyether blocks can contain units other than ethylene oxide units,such as, for example, propylene oxide or polytetrahydrofuran (whichleads to polytetramethylene glycol sequences). It is also possible touse simultaneously PEG blocks, i.e., those consisting of ethylene oxideunits, polypropylene glycol (PPG) blocks, i.e. those consisting ofpropylene oxide units, and poly(tetramethylene ether)glycol (PTMG)blocks, i.e. those consisting of tetramethylene glycol units, also knownas polytetrahydrofuran. PPG or PTMG blocks are advantageously used. Theamount of polyether blocks in these copolymers containing polyamide andpolyether blocks can be from about 10 weight percent to about 50 weightpercent of the copolymer, or from about 35 weight percent to about 50weight percent.

The copolymers containing polyamide blocks and polyether blocks can beprepared by any means for attaching the polyamide blocks and thepolyether blocks. In practice, two processes are essentially used, onebeing a 2-step process and the other a one-step process.

In the two-step process, the polyamide blocks having dicarboxylic chainends are prepared first, and then, in a second step, these polyamideblocks are linked to the polyether blocks. The polyamide blocks havingdicarboxylic chain ends are derived from the condensation of polyamideprecursors in the presence of a chain-stopper dicarboxylic acid. If thepolyamide precursors are only lactams or α,ω-aminocarboxylic acids, adicarboxylic acid is added. If the precursors already comprise adicarboxylic acid, this is used in excess with respect to thestoichiometry of the diamines. The reaction usually takes place fromabout 180 to about 300 degrees C., such as from about 200 degrees toabout 290 degrees C., and the pressure in the reactor can be set fromabout 5 to about 30 bar and maintained for approximately 2 to 3 hours.The pressure in the reactor is slowly reduced to atmospheric pressureand then the excess water is distilled off, for example for one or twohours.

Once the polyamide having carboxylic acid end groups has been prepared,the polyether, the polyol and a catalyst are then added. The totalamount of polyether can be divided and added in one or more portions, ascan the catalyst. The polyether is added first and the reaction of theOH end groups of the polyether and of the polyol with the COOH endgroups of the polyamide starts, with the formation of ester linkages andthe elimination of water. Water is removed as much as possible from thereaction mixture by distillation and then the catalyst is introduced inorder to complete the linking of the polyamide blocks to the polyetherblocks. This second step takes place with stirring, preferably under avacuum of at least 50 millibar (5000 Pascals) at a temperature such thatthe reactants and the copolymers obtained are in the molten state. Byway of example, this temperature can be from about 100 to about 400degrees C., such as from about 200 to about 250 degrees C. The reactionis monitored by measuring the torque exerted by the polymer melt on thestirrer or by measuring the electric power consumed by the stirrer. Theend of the reaction is determined by the value of the torque or of thetarget power. The catalyst is defined as being any product whichpromotes the linking of the polyamide blocks to the polyether blocks byesterification. The catalyst can be a derivative of a metal (M) chosenfrom the group formed by titanium, zirconium and hafnium. The derivativecan be prepared from a tetraalkoxides consistent with the generalformula M(OR)₄, in which M represents titanium, zirconium or hafnium andR, which can be identical or different, represents linear or branchedalkyl radicals having from 1 to 24 carbon atoms.

The catalyst can comprise a salt of the metal (M), particularly the saltof (M) and of an organic acid and the complex salts of the oxide of (M)and/or the hydroxide of (M) and an organic acid. The organic acid can beformic acid, acetic acid, propionic acid, butyric acid, valeric acid,caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid,cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, salicylicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, maleic acid, fumaric acid, phthalic acid or crotonic acid. Theorganic acid can be an acetic acid or a propionic acid. M can bezirconium and such salts are called zirconyl salts, e.g., thecommercially available product sold under the name zirconyl acetate.

The weight proportion of catalyst can vary from about 0.01 to about 5percent of the weight of the mixture of the dicarboxylic polyamide withthe polyetherdiol and the polyol. The weight proportion of catalyst canvary from about 0.05 to about 2 percent of the weight of the mixture ofthe dicarboxylic polyamide with the polyetherdiol and the polyol.

In the one-step process, the polyamide precursors, the chain stopper andthe polyether are blended together; what is then obtained is a polymerhaving essentially polyether blocks and polyamide blocks of highlyvariable length, but also the various reactants that have reactedrandomly, which are distributed randomly along the polymer chain. Theyare the same reactants and the same catalyst as in the two-step processdescribed above. If the polyamide precursors are only lactams, it isadvantageous to add a little water. The copolymer has essentially thesame polyether blocks and the same polyamide blocks, but also a smallportion of the various reactants that have reacted randomly, which aredistributed randomly along the polymer chain. As in the first step ofthe two-step process described above, the reactor is closed and heated,with stirring. The pressure established is from about 5 to about 30 bar.When the pressure no longer changes, the reactor is put under reducedpressure while still maintaining vigorous stirring of the moltenreactants. The reaction is monitored as previously in the case of thetwo-step process.

The proper ratio of polyamide to polyether blocks can be found in asingle poly(ether block amide), or a blend of two or more differentcomposition poly(ether block amide)s can be used with the proper averagecomposition. It can be useful to blend a block copolymer having a highlevel of polyamide groups with a block copolymer having a higher levelof polyether blocks, to produce a blend having an average level ofpolyether blocks of about 20 to about 40 weight percent of the totalblend of poly(amid-block-ether) copolymers, or about 30 to about 35weight percent. The copolymer can comprise a blend of two differentpoly(ether-block-amide)s comprising at least one block copolymer havinga level of polyether blocks below 35 weight percent, and a secondpoly(ether-block-amide) having at least 45 weight percent of polyetherblocks.

Exemplary commercially available copolymers include, but are not limitedto, those available under the tradenames of “VESTAMID” (EvonikIndustries, Essen, Germany); “PLATAMID” (Arkema, Colombes, France),e.g., product code H2694; “PEBAX” (Arkema), e.g., product code “PEBAXMH1657” and “PEBAX MV1074”; “PEBAX RNEW” (Arkema); “GRILAMID”(EMS-Chemie AG, Domat-Ems, Switzerland), or also to other similarmaterials produced by various other suppliers.

The polyamide can be physically crosslinked through, e.g., nonpolar orpolar interactions between the polyamide groups of the polymers. Inexamples where the polyamide is a copolyamide, the copolyamide can bephysically crosslinked through interactions between the polyamidegroups, and optionally by interactions between the copolymer groups.When the co-polyamide is physically crosslinked through interactionsbetween the polyamide groups, the polyamide segments can form theportion of the polymer referred to as the hard segment, and copolymersegments can form the portion of the polymer referred to as the softsegment. For example, when the copolyamide is a poly(ether-block-amide),the polyamide segments form the hard segments of the polymer, andpolyether segments form the soft segments of the polymer. Therefore, insome examples, the polymer can include a physically crosslinkedpolymeric network having one or more polymer chains with amide linkages.

The polyamide segment of the co-polyamide can include polyamide-11 orpolyamide-12 and the polyether segment can be a segment selected fromthe group consisting of polyethylene oxide, polypropylene oxide, andpolytetramethylene oxide segments, and combinations thereof.

The polyamide can be partially or fully covalently crosslinked, aspreviously described herein. In some cases, the degree of crosslinkingpresent in the polyamide is such that, when it is thermally processed,e.g., in the form of a yarn or fiber to form the articles of the presentdisclosure, the partially covalently crosslinked thermoplastic polyamideretains sufficient thermoplastic character that the partially covalentlycrosslinked thermoplastic polyamide is melted during the processing andre-solidifies. In other cases, the crosslinked polyamide is a thermosetpolymer.

Polyesters

The composition and/or the elastomeric material can comprise apolyester. The article comprising the elastomeric material can furtherone or more components comprising a polyester. The polyester cancomprise a thermoplastic polyester, or a thermoset polyester.Additionally, the polyester can be an elastomeric polyester, including athermoplastic polyester or a thermoset elastomeric polyester. Thepolyester can be formed by reaction of one or more carboxylic acids, orits ester-forming derivatives, with one or more bivalent or multivalentaliphatic, alicyclic, aromatic or araliphatic alcohols or a bisphenol.The polyester can be a polyester homopolymer having repeating polyestersegments of the same chemical structure. Alternatively, the polyestercan comprise a number of polyester segments having different polyesterchemical structures (e.g., polyglycolic acid segments, polylactic acidsegments, polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, etc.). The polyester segments havingdifferent chemical structure can be arranged randomly, or can bearranged as repeating blocks.

Exemplary carboxylic acids that can be used to prepare a polyesterinclude, but are not limited to, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedicarboxylic acid, undecane dicarboxylic acid, terephthalic acid,isophthalic acid, alkyl-substituted or halogenated terephthalic acid,alkyl-substituted or halogenated isophthalic acid, nitro-terephthalicacid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl thioetherdicarboxylic acid, 4,4′-diphenyl sulfone-dicarboxylic acid,4,4′-diphenyl alkylenedicarboxylic acid, naphthalene-2,6-dicarboxylicacid, cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylicacid. Exemplary diols or phenols suitable for the preparation of thepolyester include, but are not limited to, ethylene glycol, diethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol,1,10-decanediol, 1,2-propanediol, 2,2-dimethyl-1,3-propanediol,2,2,4-trimethylhexanediol, p-xylenediol, 1,4-cyclohexanediol,1,4-cyclohexane dimethanol, and bis-phenol A.

The polyester can be a polybutylene terephthalate (PBT), apolytrimethylene terephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), a liquid crystal polyester, or a blendor mixture of two or more of the foregoing.

The polyester can be a co-polyester (i.e., a co-polymer includingpolyester segments and non-polyester segments). The co-polyester can bean aliphatic co-polyester (i.e., a co-polyester in which both thepolyester segments and the non-polyester segments are aliphatic).Alternatively, the co-polyester can include aromatic segments. Thepolyester segments of the co-polyester can comprise or consistessentially of polyglycolic acid segments, polylactic acid segments,polycaprolactone segments, polyhydroxyalkanoate segments,polyhydroxybutyrate segments, or any combination thereof. The polyestersegments of the co-polyester can be arranged randomly, or can bearranged as repeating blocks.

For example, the polyester can be a block co-polyester having repeatingblocks of polymeric units of the same chemical structure which arerelatively harder (hard segments), and repeating blocks of the samechemical structure which are relatively softer (soft segments). In blockco-polyesters, including block co-polyesters having repeating hardsegments and soft segments, physical crosslinks can be present withinthe blocks or between the blocks or both within and between the blocks.The polymer can comprise or consist essentially of an elastomericco-polyester having repeating blocks of hard segments and repeatingblocks of soft segments.

The non-polyester segments of the co-polyester can comprise or consistessentially of polyether segments, polyamide segments, or both polyethersegments and polyamide segments. The co-polyester can be a blockco-polyester, or can be a random co-polyester. The co-polyester can beformed from the polycondensation of a polyester oligomer or prepolymerwith a second oligomer prepolymer to form a block copolyester.Optionally, the second prepolymer can be a hydrophilic prepolymer. Forexample, the co-polyester can be formed from the polycondensation ofterephthalic acid or naphthalene dicarboxylic acid with ethylene glycol,1,4-butanediol, or 1,3-propanediol. Examples of co-polyesters includepolyethylene adipate, polybutylene succinate,poly(3-hydroxbutyrate-co-3-hydroxyvalerate), polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenenapthalate, and combinations thereof. The co-polyamide can comprise orconsist of polyethylene terephthalate.

The polyester can be a block copolymer comprising segments of one ormore of polybutylene terephthalate (PBT), a polytrimethyleneterephthalate, a polyhexamethylene terephthalate, apoly-1,4-dimethylcyclohexane terephthalate, a polyethylene terephthalate(PET), a polyethylene isophthalate (PEI), a polyarylate (PAR), apolybutylene naphthalate (PBN), and a liquid crystal polyester. Forexample, a suitable polyester that is a block copolymer can be a PET/PEIcopolymer, a polybutylene terephthalate/tetraethylene glycol copolymer,a polyoxyalkylenediimide diacid/polybutylene terephthalate copolymer, ora blend or mixture of any of the foregoing.

The polyester can be a biodegradable resin, for example, a copolymerizedpolyester in which poly(a-hydroxy acid) such as polyglycolic acid orpolylactic acid is contained as principal repeating units.

The disclosed polyesters can be prepared by a variety ofpolycondensation methods known to the skilled artisan, such as a solventpolymerization or a melt polymerization process.

Polyolefins

The composition and/or elastomeric material can comprise a polyolefin.The article comprising the elastomeric material can further one or morecomponents comprising a polyolefin. The polyolefin can be athermoplastic polyolefin or a thermoset polyolefin. Additionally, thepolyolefin can be an elastomeric polyolefin, including a thermoplasticelastomeric polyolefin or a thermoset elastomeric polyolefin. Exemplarypolyolefins can include polyethylene, polypropylene, and olefinelastomers (e.g., metallocene-catalyzed block copolymers of ethylene andα-olefins having 4 to about 8 carbon atoms). The polyolefin can be apolymer comprising a polyethylene, an ethylene-α-olefin copolymer, anethylene-propylene rubber (EPDM), a polybutene, a polyisobutylene, apoly-4-methylpent-1-ene, a polyisoprene, a polybutadiene, aethylene-methacrylic acid copolymer, and an olefin elastomer such as adynamically cross-linked polymer obtained from polypropylene (PP) and anethylene-propylene rubber (EPDM), and blends or mixtures of theforegoing. Further exemplary polyolefins include polymers ofcycloolefins such as cyclopentene or norbornene.

It is to be understood that polyethylene, which optionally can becrosslinked, is inclusive a variety of polyethylenes, including lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE), medium density polyethylene (MDPE), high densitypolyethylene (HDPE), high density and high molecular weight polyethylene(HDPE-HMW), high density and ultrahigh molecular weight polyethylene(HDPE-UHMW), and blends or mixtures of any the foregoing polyethylenes.A polyethylene can also be a polyethylene copolymer derived frommonomers of monolefins and diolefins copolymerized with a vinyl, acrylicacid, methacrylic acid, ethyl acrylate, vinyl alcohol, and/or vinylacetate. Polyolefin copolymers comprising vinyl acetate-derived unitscan be a high vinyl acetate content copolymer, e.g., greater than about50 weight percent vinyl acetate-derived composition.

The polyolefin can be formed through free radical, cationic, and/oranionic polymerization by methods well known to those skilled in the art(e.g., using a peroxide initiator, heat, and/or light). The disclosedpolyolefin can be prepared by radical polymerization under high pressureand at elevated temperature. Alternatively, the polyolefin can beprepared by catalytic polymerization using a catalyst that normallycontains one or more metals from group IVb, Vb, VIb or VIII metals. Thecatalyst usually has one or more than one ligand, typically oxides,halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/oraryls that can be either p- or s-coordinated complexed with the groupIVb, Vb, VIb or VIII metal. The metal complexes can be in the free formor fixed on substrates, typically on activated magnesium chloride,titanium(III) chloride, alumina or silicon oxide. The metal catalystscan be soluble or insoluble in the polymerization medium. The catalystscan be used by themselves in the polymerization or further activatorscan be used, typically a group Ia, IIa and/or IIIa metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes.The activators can be modified conveniently with further ester, ether,amine or silyl ether groups.

Suitable polyolefins can be prepared by polymerization of monomers ofmonolefins and diolefins as described herein. Exemplary monomers thatcan be used to prepare the polyolefin include, but are not limited to,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixturesthereof.

Suitable ethylene-α-olefin copolymers can be obtained bycopolymerization of ethylene with an α-olefin such as propylene,butene-1, hexene-1, octene-1,4-methyl-1-pentene or the like havingcarbon numbers of 3 to 12.

Suitable dynamically cross-linked polymers can be obtained bycross-linking a rubber component as a soft segment while at the sametime physically dispersing a hard segment such as PP and a soft segmentsuch as EPDM by using a kneading machine such as a Banbury mixer and abiaxial extruder.

The polyolefin can be a mixture of polyolefins, such as a mixture of twoor more polyolefins disclosed herein above. For example, a suitablemixture of polyolefins can be a mixture of polypropylene withpolyisobutylene, polypropylene with polyethylene (for example PP/HDPE,PP/LDPE) or mixtures of different types of polyethylene (for exampleLDPE/HDPE).

The polyolefin can be a copolymer of suitable monolefin monomers or acopolymer of a suitable monolefin monomer and a vinyl monomer. Exemplarypolyolefin copolymers include ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

The polyolefin can be a polypropylene homopolymer, a polypropylenecopolymers, a polypropylene random copolymer, a polypropylene blockcopolymer, a polyethylene homopolymer, a polyethylene random copolymer,a polyethylene block copolymer, a low density polyethylene (LDPE), alinear low density polyethylene (LLDPE), a medium density polyethylene,a high density polyethylene (HDPE), or blends or mixtures of one or moreof the preceding polymers.

The polyolefin can be a polypropylene. The term “polypropylene,” as usedherein, is intended to encompass any polymeric composition comprisingpropylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as ethylene, butylene, and the like). Such a term also encompassesany different configuration and arrangement of the constituent monomers(such as atactic, syndiotactic, isotactic, and the like). Thus, the termas applied to fibers is intended to encompass actual long strands,tapes, threads, and the like, of drawn polymer. The polypropylene can beof any standard melt flow (by testing); however, standard fiber gradepolypropylene resins possess ranges of Melt Flow Indices between about 1and 1000.

The polyolefin can be a polyethylene. The term “polyethylene,” as usedherein, is intended to encompass any polymeric composition comprisingethylene monomers, either alone or in mixture or copolymer with otherrandomly selected and oriented polyolefins, dienes, or other monomers(such as propylene, butylene, and the like). Such a term alsoencompasses any different configuration and arrangement of theconstituent monomers (such as atactic, syndiotactic, isotactic, and thelike). Thus, the term as applied to fibers is intended to encompassactual long strands, tapes, threads, and the like, of drawn polymer. Thepolyethylene can be of any standard melt flow (by testing); however,standard fiber grade polyethylene resins possess ranges of Melt FlowIndices between about 1 and 1000.

The composition and/or the elastomeric material can further comprise oneor more processing aids. The article comprising the elastomeric materialcan further one or more components comprising one or more processingaids. The processing aid can be a non-polymeric material. Theseprocessing aids can be independently selected from the group including,but not limited to, curing agents, initiators, plasticizers, moldrelease agents, lubricants, antioxidants, flame retardants, dyes,pigments, reinforcing and non-reinforcing fillers, fiber reinforcements,and light stabilizers

The composition can be a thermoplastic composition. For example, thethermoplastic composition can comprise one or more of thermoplasticpolyurethanes, thermoplastic polyesters, thermoplastic polyamides,thermoplastic polyolefins, or a co-polymer or combination including ofany of the foregoing.

The thermoplastic composition can have a softening or melting point ofabout 80° C. to about 140° C. A temperature of the thermoplasticcomposition can be increased to a temperature at or above creeprelaxation temperature (T_(cr)), Vicat softening temperature (T_(vs)),heat deflection temperature (T_(hd)), and/or melting temperature(T_(m)). In an aspect, the layers or structure can be attached using thethermoplastic composition while the temperature is maintained at orabove the creep relaxation temperature, the heat deflection temperature,the Vicat softening temperature, or the melting temperature, of thethermoplastic composition. The layers or structure can be attached usingthe thermoplastic composition after the temperature of the thermoplasticcomposition is allowed to drop below the creep relaxation temperature,the heat deflection temperature, the Vicat softening temperature, or themelting temperature of the thermoplastic composition, as long as thethermoplastic composition only partially re-solidified, it can be usedto attached the structure or the layers.

In general, the thermoplastic composition can have a creep relaxationtemperature (T_(cr)) of about 80° C. to about 140° C., or from about 90°C. to about 130° C., or about 100° C. to about 120° C. In general, thethermoplastic composition can have a Vicat softening temperature(T_(vs)) of about 80° C. to about 140° C., or from about 90° C. to about130° C., or about 100° C. to about 120° C. In general, the thermoplasticcomposition can have a heat deflection temperature (T_(hd)) of about 80°C. to about 140° C., or from about 90° C. to about 130° C., or about100° C. to about 120° C. In general, the thermoplastic composition canhave a melting temperature (T_(m)) of about 80° C. to about 140° C., orfrom about 90° C. to about 130° C., or about 100° C. to about 120° C.

The elastomeric material is a thermoset composition. The thermosetcomposition can comprise a thermoset polyurethane polymer, thermosetpolyurea polymer, thermoset polyamide polymer, thermoset polyolefinpolymer, or thermoset silicone polymer, or a co-polymer or combinationincluding any of the foregoing.

In addition to the elastomeric material, the articles of the presentdisclosure can comprise a polymeric foam composition. For example, thepolymeric foam composition can include a polyolefin foam, polyurethanefoam, an ethylene-vinyl acetate (EVA) foam, a propylene foam, or acombination thereof. The polymeric foam composition can include a blendwith one or more additional materials to impart additionalcharacteristics or properties to the composition. The polymeric foamcomposition can include one or more other components. A foam compositioncan include a chemical blowing agent such as a carbonate, bicarbonate,carboxylic acid, azo compound, isocyanate, persulfate, peroxide, or acombination thereof. The foam composition can include about 1 parts perhundred resin to about 10 parts per hundred resin, or about 3 parts perhundred resin to about 7 parts per hundred resin of the chemical blowingagent. The chemical blowing agent has a decomposition temperature ofabout 130° C. to about 160° C., or about 135° C. to about 155° C. A foamcomposition can include a crosslinking agent such as an aliphaticunsaturated amide, such as methylenebisacryl- or -methacrylamide orethylenebisacrylamide; aliphatic esters of polyols or alkoxylatedpolyols with ethylenically unsaturated acids, such as di(meth)acrylatesor tri(meth)acrylates of butanediol or ethylene glycol, polyglycols ortrimethylolpropane; di- and tri-acrylate esters of trimethylolpropane;acrylate and methacrylate esters of glycerol and pentaerythritol; allylcompounds, such as allyl (meth)acrylate, alkoxylated allyl(meth)acrylate, triallyl cyanurate, triallyl isocyanurate, maleic aciddiallyl ester, poly-allyl esters, vinyl trimethoxysilane, vinyltriethoxysilane, polysiloxane comprising at least two vinyl groups,tetraallyloxyethane, tetraallyloxyethane, triallylamine, andtetraallylethylenediamine; or a mixture thereof. The foam compositioncan include about 0.1 parts per hundred resin to about 1.5 parts perhundred resin, or about 0.3 parts per hundred resin to about 0.8 partsper hundred resin of the crosslinking agent. A foam composition caninclude zinc oxide. The zinc oxide can be present from about 0.1 partsper hundred resin to about 5 parts per hundred resin, or about 0.7 partsper hundred resin to about 2 parts per hundred resin. The foamcomposition can include calcium carbonate. The calcium carbonate can bepresent from about 1 parts per hundred resin to about 10 parts perhundred resin, or from about 3 parts per hundred resin to about 7 partsper hundred resin. The foam composition can include a dye or pigment.The dye or pigment is present in the resin composition at a level ofabout 0 parts per hundred resin to about 10 parts per hundred resin, orabout 0.5 parts per hundred resin to about 5 parts per hundred resinbased upon the weight of the resin composition.

When the elastomeric materials an article of footwear or a component ofan article of footwear, such as an outsole of an article of footwear,the elastomeric material can include an ingredient providing additionalabrasion resistance and durability as necessary or desirable for use insuch articles. The composition can pass a flex test pursuant to the ColdRoss Flex Test as described further herein. The composition can havesuitable abrasion loss when measured pursuant to ASTM D 5963-97, asdescribed further herein. The composition can have an abrasion loss ofabout 0.07 cubic centimeters (cm³) to about 0.1 cubic centimeters (cm³),about 0.08 cubic centimeters (cm³) to about 0.1 cubic centimeters (cm³),or about 0.08 cubic centimeters (cm³) to about 0.11 cubic centimeters(cm³) pursuant to ASTM D 5963-97a using the Material Sampling Procedure.

A component of the article can include a variety of polyolefincopolymers. The copolymers can be alternating copolymers or randomcopolymers or block copolymers or graft copolymers. The copolymers canbe random copolymers. The copolymer can include a plurality of repeatunits, with each of the plurality of repeat units individually derivedfrom an alkene monomer having about 1 to about 6 carbon atoms. Thecopolymer can include a plurality of repeat units, with each of theplurality of repeat units individually derived from a monomer selectedfrom the group consisting of ethylene, propylene, 4-methyl-1-pentene,1-butene, 1-octene, and a combination thereof.

The polyolefin copolymer can be a random copolymer of a first pluralityof repeat units and a second plurality of repeat units, and each repeatunit in the first plurality of repeat units is derived from ethylene andthe each repeat unit in the second plurality of repeat units is derivedfrom a second olefin. The second olefin can be an alkene monomer havingabout 1 to about 6 carbon atoms. The second olefin can includepropylene, 4-methyl-1-pentene, 1-butene, or other linear or branchedterminal alkenes having about 3 to 12 carbon atoms. The polyolefincopolymer can contain about 80 percent to about 99 percent, about 85percent to about 99 percent, about 90 percent to about 99 percent, orabout 95 percent to about 99 percent polyolefin repeat units by weightbased upon a total weight of the polyolefin copolymer. The polyolefincopolymer can consist essentially of polyolefin repeat units. Thepolymers in the polymeric composition can consist essentially ofpolyolefin copolymers.

The polyolefin copolymer can include ethylene, i.e. can include repeatunits derived from ethylene. The polyolefin copolymer can include about1 percent to about 5 percent, about 1 percent to about 3 percent, about2 percent to about 3 percent, or about 2 percent to about 5 percentethylene by weight based upon a total weight of the polyolefincopolymer.

The polyolefin copolymer can be substantially free of polyurethanes. Thepolymer chains of the polyolefin copolymer can be substantially free ofurethane repeat units. The polymeric composition can be substantiallyfree of polymer chains including urethane repeat units. The polyolefincopolymer can be substantially free of polyamide groups. The polymerchains of the polyolefin copolymer can be substantially free of amiderepeat units. The polymeric composition can be substantially free ofpolymer chains including amide repeat units.

The polyolefin copolymer can include polypropylene or can be apolypropylene copolymer. The polymer component of the polymericcomposition (i.e., the portion of the polymeric composition that isformed by all of the polymers present in the composition) can consistessentially of polypropylene copolymers. The polypropylene copolymer caninclude a random copolymer, e.g. a random copolymer of ethylene andpropylene. The polypropylene copolymer can include about 80 percent toabout 99 percent, about 85 percent to about 99 percent, about 90 percentto about 99 percent, or about 95 percent to about 99 percent propylenerepeat units by weight based upon a total weight of the polypropylenecopolymer. The polypropylene copolymer can include about 1 percent toabout 5 percent, about 1 percent to about 3 percent, about 2 percent toabout 3 percent, or about 2 percent to about 5 percent ethylene byweight based upon a total weight of the polypropylene copolymer. Thepolypropylene copolymer can be a random copolymer including about 2percent to about 3 percent of a first plurality of repeat units byweight and about 80 percent to about 99 percent by weight of a secondplurality of repeat units based upon a total weight of the polypropylenecopolymer.

The composition forming the component comprised of the polyolefincopolymer can include a resin modifier that can improved flexuraldurability while maintaining suitable abrasion resistance. For example,the composition including the resin modifier can pass a flex testpursuant to the Cold Ross Flex Test using the Plaque Sampling Procedure,and at the same time, the composition can still have a suitable abrasionloss when measured pursuant to ASTM D 5963-97a using the MaterialSampling Procedure. The composition including the resin modifier canhave no significant change in the abrasion loss as compared to anabrasion loss of a substantially similar composition without the resinmodifier, when measured pursuant to ASTM D 5963-97a using the MaterialSampling Procedure. A change in abrasion loss, as used herein, is saidto not be significant when the change is about 30 percent, about 25percent, about 20 percent, about 15 percent, about 10 percent, or lesswhen measured pursuant to ASTM D 5963-97a using the Material SamplingProcedure.

The combination of abrasion resistance and flexural durability can berelated to the overall crystallinity of the composition comprising thepolyolefin copolymer. The composition can have a percent crystallizationof about 45 percent, about 40 percent, about 35 percent, about 30percent, about 25 percent or less when measured according to theDifferential Scanning calorimeter (DSC) Test using the Material SamplingProcedure. The resin modifier can provide a decrease in the percentcrystallinity of the composition, as compared to a substantially similarcomposition without the resin modifier. The composition can have apercent crystallization that is at least 6, at least 5, at least 4, atleast 3, or at least 2 percentage points less than a percentcrystallization a substantially similar composition without the resinmodifier when measured according to the Differential Scanningcalorimeter (DSC) Test using the Material Sampling Procedure.

The effective amount of the resin modifier can be about 5 percent toabout 30 percent, about 5 percent to about 25 percent, about 5 percentto about 20 percent, about 5 percent to about 15 percent, about 5percent to about 10 percent, about 10 percent to about 15 percent, about10 percent to about 20 percent, about 10 percent to about 25 percent, orabout 10 percent to about 30 percent by weight based upon a total weightof the composition. The effective amount of the resin modifier can beabout 20 percent, about 15 percent, about 10 percent, about 5 percent,or less by weight based upon a total weight of the composition.

The resin modifier can include a variety of known resin modifiers. Theresin modifier can be a metallocene catalyzed copolymer primarilycomposed of isotactic propylene repeat units with about 11 percent byweight-15 percent by weight of ethylene repeat units based on a totalweight of metallocene catalyzed copolymer randomly distributed along thecopolymer. The resin modifier can include about 10 percent to about 15percent ethylene repeat units by weight based upon a total weight of thepolymeric resin modifier. The resin modifier can be a copolymercontaining isotactic propylene repeat units and ethylene repeat units.

Now having described various aspects of the present disclosure,additional detail regarding methods of making and using the elastomericmaterial are provided. In an aspect, a method of making an article(e.g., an article of footwear, an article of apparel, or an article ofsporting equipment, or component of each) can include attaching (e.g.,affixing, coupling, adhering, bonding, etc.) the elastomeric material toa surface of the article. In an example and for illustrative purposes asdescribed below, a first component and a second component including theelastomeric material are attached to one another, thereby forming thearticle.

In regard to an article of footwear, the first component can be an upperfor an article of footwear and/or a sole for an article of footwear. Forexample, the step of attaching can include attaching the sole and thesecond component such that the externally-facing layer of theelastomeric material forms at least a portion of a side of the solewhich is configured to be ground-facing. The footwear can includetraction elements, where the elastomeric material is positioned betweenthe traction elements and optionally on the sides of the tractionelements, but not on the side(s) configured to touch the ground.

Referring once again to FIGS. 2F and 2G, the outsole 15 of the shoe 75may be engaged with or attached to the upper 25 being directly adheredthereto. However, when desirable, a portion of the outsole may beattached to the upper 25 through the use of additional meansconventionally known or used in the construction of footwear 75, such asthrough the use of cements or adhesives, by mechanical connectors, andby sewing or stitching, to name a few.

Referring now to FIG. 5A, according to another aspect of the presentdisclosure, a method 100 is provided through which an article offootwear can be formed. While an article of footwear is used forexemplary purposes, it is to be understood that this method appliesgenerally to other types of articles. This method 100 may comprise,consist of, or consist essentially of providing or receiving 105 a firstcomponent, such as an upper for an article of footwear, optionallycomprising a textile; providing or receiving 110 a second component,such as an outsole for an article of footwear, that includes anelastomeric material that defines an externally facing side of thearticle. The elastomeric material includes a mixture of a polymerichydrogel and a cured rubber; and coupling 115 the first component andthe second component together. The polymeric hydrogel is distributedthroughout the cured rubber and at least a portion of the polymerichydrogel in the elastomeric material is physically entrapped by thecured rubber. When desirable, the method may further include providingor receiving 120 a third component such as a midsole; and attaching 125the third component to the second component and/or the first componentprior to the attaching of the second component to the first component,such that the third component resides between the second component andthe first component.

The method may also comprise fully curing 137 the rubber, when therubber is only partially cured in forming the second component. Thecuring is accomplished through the occurrence of one or morecrosslinking or polymerizing mechanisms. The occurrence of suchcrosslinking mechanisms may be induced by sulfur or peroxide curing ofthe partially cured rubber or by exposing the partially cured rubber toactinic radiation at a concentration and for a duration to at leastpartially cure the mixture.

The step of receiving 110 the second component may comprise a method 101of forming an uncured composition 107. This method 101 comprisesproviding an uncured rubber 126 and providing a hydrogel 127. Then,mixing 130 the hydrogel with the uncured rubber to distribute thepolymeric hydrogel throughout the uncured rubber to form a mixturecomposition. The method 101 may further comprise shaping or forming 132into a sheet or molding the composition into a shape, such as the shapeof an outsole, by subjecting the composition to an extrusion process, amolding process, or a combination thereof. When desirable, thecomposition is at least partially cured 137 to form an elastomericmaterial.

For the purpose of this disclosure, the term “partially cured” denotesthe occurrence of at least about 1 percent, alternatively, at leastabout 5 percent of the total polymerization required to achieve asubstantially full cure. The term “fully cured” is intended to mean asubstantially full cure in which the degree of curing is such that thephysical properties of the cured material do not noticeably change uponfurther exposure to conditions that induce curing (e.g., temperature,pressure, presence of curing agents, etc.).

According to another aspect of the present disclosure, a method 102 ofpreparing an elastomeric material 129 for use in forming an article or acomponent in a finished article such as an article of apparel orsporting equipment is provided. Referring now to FIG. 5B, the method 102comprises the steps of providing 107 a composition. This composition mayinclude a mixture of a polymeric hydrogel and an uncured rubber. Theuncured composition may be at least partially cured 119 to form anelastomeric material for use in a component, such as a component of anarticle of apparel or sporting equipment. The polymeric hydrogel ispresent in the elastomeric material in an amount that ranges from about5 weight percent to about 85 weight percent based on the overall weightof resin component (i.e., the total weight of all the polymericmaterials present) of the elastomeric material. Optionally, theelastomeric material may be formed 132 into a component, such that theelastomeric material defines at least a portion of a surface of thecomponent that is configured to be externally facing.

According to another aspect of the present disclosure, a method 103 forforming an article or a component of an article 135 for use in afinished article, such as an article of apparel or sporting equipment isprovided. Referring now to FIG. 5C, this method 103 comprises the stepsof providing or receiving 129 an uncured composition or an elastomericmaterial. When desirable, the uncured composition or the elastomericmaterial may be prepared according to the previously described methods101 and 102. The article or component of the article is then formed 132,such that the uncured composition or the elastomeric material defines atleast a portion of a surface that is configured to be externally-facingwhen the component or the article is present in a finished article. Theuncured composition is at least partially cured to form the elastomericmaterial and/or the elastomeric material is partially or fully cured137, such that it exhibits a water uptake rate of 10 g/m²√min to 120g/m²√min as measured in the Water Uptake Rate Test over a soaking timeof 9 minutes using the Component Sampling Procedure.

According to yet another aspect of the present disclosure, a method 104for manufacturing a finished article is provided. Referring now to FIG.5D, the method 104 comprises providing two or more articles orcomponents of an article 141. At least one component comprises anelastomeric material 135, wherein the elastomeric material includes amixture of a cured rubber and a polymeric hydrogel. The polymerichydrogel may comprise an aliphatic polyurethane (TPU) resin or apolyether block amide resin, such that the hydrogel is present in anamount ranging from about 5 weight percent to about 85 weight percentbased on the overall weight of the resin component (i.e., the totalweight of all the polymeric materials present) of the elastomericmaterial. The elastomeric material may be either partially cured orfully cured. The two or more components are attached to one another(e.g., coupled together) 143, such that the elastomeric material definesat least a portion of a surface of at least one component that isconfigured to be externally facing when this at least one component ispresent in a finished article. The elastomeric material exhibits a watercycling weight loss from about 0 weight percent to about 15 weightpercent as measured pursuant to the Water Cycling Test and using theMaterial Sampling Procedure or the Article Sampling Procedure.

When desirable, the method 104 may further comprise exposing 145 thefinished article or the component of the finished article that comprisesthe elastomeric material to actinic radiation at a concentration and fora duration of time sufficient to fully cure the elastomeric material.Fully curing 145 the elastomeric material may be done before, during, orafter the step of coupling 143 the two or more components together.

In the step 130 (see FIG. 5A) in which the hydrogel and the uncuredrubber are mixed, the materials are mixed together until they aresubstantially blended. The mixing may be accomplished using, withoutlimitation, an intermeshing-type internal mixer, a tangential-typeinternal mixer, a planetary mixer, a mill, a ribbon blender, a coneblender, a screw blender, a drum blender, a Banbury mixer, or the like.More specifically, the hydrogel and uncured rubber may be compounded inconventional rubber processing equipment. In a typical procedure, allcomponents of the composition are weighed out. The uncured rubber, thehydrogel (e.g., hydrophilic thermoplastic polyurethane), and anyadditives are then compounded in a conventional mixer such as a Banburymixer. If desired, the compounded composition may then be further mixedon a roller mill. At this time, it is possible to add other additives,such as pigments (e.g., carbon black, etc.). The composition may beallowed to mature for a period of hours prior to the addition of a curesystem, alternatively, the additives that comprise the cure system maybe added immediately on the roller mill.

In the step 132 (see FIGS. 5A and 5B) in which the article or componentof an article (e.g., an outsole, etc.) is formed, the process of formingthe article or component may include, but not be limited to, the use ofone or more of an extrusion process, a calendaring process, an injectionmolding process, a compression molding process, a thermoforming process,or the like.

In the step 137 (see FIGS. 5A and 5C) in which the elastomeric materialis at least partially cured, alternatively, fully cured, the curing isaccomplished by the occurrence of one or more crosslinking mechanisms.These crosslinking mechanisms may occur, without limitation, via the useof crosslinking agents that are thermally initiated, such assulfur-based or peroxide-based crosslinking agents or initiators thatcrosslink radiation curable rubbers upon exposure of the rubber toactinic radiation at a centration and for a duration of time sufficientto achieve the desired degree of cure. According to another aspect ofthe present disclosure, the use of an article or a component of anarticle compositionally comprising an elastomeric material to prevent orreduce soil accumulation on the article or component of a finishedarticle of apparel or sporting equipment is described. The use involvesincorporating the article or component as an externally-facing surfacein a finished article in order to prevent or reduce soil accumulation onthe component and article. The component or article retains at least 5percent less soil by weight; alternatively, at least 10 percent lesssoil by weight, as compared to a conventional component or article thatis identical except that the externally-facing surface of theconventional component or article is substantially free of anelastomeric material that comprises a mixture of the hydrogel and thecured rubber.

The method of forming an article can comprise forming the article from afirst component including a first material and a second componentincluding a second material comprising an uncured composition or anelastomeric material as described herein. The first material can form asubstantial majority of a volume of the first component, or can be acoating or tie layer present on an exterior surface or side of the firstcomponent. When the first component comprises a first material includinga crosslinkable polymer, a polymer precursor, or both, attaching thefirst and second components can comprise curing the first material incontact with the second material.

In one example, the first material can be a first uncured composition ora first elastomeric material according to the present disclosure. Forexample, the first material can comprise substantially the samerubber(s), can comprise the substantially the same polymerichydrogel(s), can comprise substantially the same concentration ofrubber(s), can comprise substantially the same concentrations of andpolymeric hydrogel(s), or any combination thereof, as the secondmaterial. Alternatively or additionally, the first material and thesecond material can comprise different types of polymeric hydrogel(s),or different concentrations of polymeric hydrogel(s), or differentcolorant(s), or different concentrations of colorant(s), or anycombination thereof. For example, the first material and the secondmaterial can differ only in the concentration of polymeric hydrogel(s),or only in the concentration of colorant(s), or in both theconcentration of polymeric hydrogel(s) and colorant(s).

In another example, the first material can be substantially free of apolymeric hydrogel but can include a crosslinkable polymeric material,or a polymerizable material, so that it is possible to form crosslinkingbonds or polymer bonds between the first material and the secondmaterial.

The crosslinkable polymeric material can include one or more elastomericpolymers such as uncured or partially cured rubber, or polymerprecursors such as one or more types of monomers. In one example, thefirst material can comprise the same uncured or partially curedrubber(s) as the second elastomeric material, but the first material issubstantially free of a polymeric hydrogel. In another example, thefirst material can comprise one or more uncured or partially curedrubber(s) which are harder than the uncured or partially cured rubber(s)of the second material. In this example, the harder first material canbe used to form traction elements such as lugs. In these examples, whereboth the first and second materials comprises crosslinkable orpolymerizable materials, curing the first material and the secondmaterial while in contact with each other can form chemical bonds (e.g.,crosslinking bonds or polymer bonds) between the first material and thesecond material, thereby attaching the first component to the secondcomponent using these chemical bonds. In some cases, it may not benecessary to further reinforce the bond using an adhesive. In thesecases, the interface between the first component and the secondcomponent can be substantially free of adhesive.

Sampling Procedures

The properties of the elastomeric material of the component in afinished article can be characterized using samples prepared andmeasured according to the Materials Sampling Procedure or the ComponentSampling Procedure. The Materials Sampling Procedure is used to obtain asample of a material of the present disclosure that is either in mediaform or isolated in a neat form (i.e., without any bonded substrate in alayered film, such as that found in the composition defined herein). Amaterial is provided in media form, when it is obtained as flakes,granules, powders, pellets, or the like. If a source of the material isnot available in a media form, the material can be cut, scraped, orground from an outsole of a footwear outsole or from a backing substrateof a co-extruded sheet or web, thereby isolating the material in mediaform. When desirable, the material in media form may be extruded as aweb or sheet having a substantially constant material thickness (within+/−10 percent of the average material thickness), and cooled to solidifythe resulting web or sheet. A sample of the material in neat form havinga surface area of 4 cm² is then cut from the resulting web or sheet foruse in testing.

The Component Sampling Procedure may include the use of one or more ofthe following sampling procedures:

(A)—Footwear Sampling Procedure

This procedure is used to obtain a sample of the elastomeric materialwhen the elastomeric material is a component of an article of footwear(e.g., bonded to an article substrate or a substrate). An articlesample, which includes the elastomeric material in a non-wet state(e.g., at about 25 degrees C. and approximately 20 percent relativehumidity) is cut from the article of footwear using a blade. Thisprocess is performed by separating the article from an associatedfootwear upper, and removing any materials from the article's topsurface (e.g., corresponding to the top surface) that can uptake waterand potentially skew the water uptake measurements of the elastomericmaterial. For example, the article's top surface can be skinned,abraded, scraped, or otherwise cleaned to remove any upper adhesives,yarns, fibers, foams, and the like that could potentially take up waterthemselves.

The resulting sample includes the component and any article substratebonded to the component, and maintains the interfacial bond between thecomponent and the associated substrate of the finished article. As such,this test can simulate how the elastomeric material will perform as partof an article of footwear. Additionally, this sample is also useful incases where the interfacial bond between the component and the substrateis less defined, such as where the elastomeric material of the componentis highly diffused into the substrate of the finished article (e.g.,with a concentration gradient).

The sample is taken at a location along the article that provides asubstantially constant thickness for the component (within plus or minus10 percent of the average thickness), such as in a forefoot region,mid-foot region, or a heel region of the article, and has a surface areaof about 4.0 square centimeters. In cases where the elastomeric materialis not present on the article in any segment having a 4.0 squarecentimeter surface area and/or where the thickness is not substantiallyconstant for a segment having a 4.0 square centimeter surface area,sample sizes with smaller cross-sectional surface areas can be taken andthe area-specific measurements are adjusted accordingly.

(B)—Apparel Sampling Procedure

This procedure is used to obtain a sample of the elastomeric materialwhen the elastomeric material is present as a component in a finishedarticle of apparel (e.g., a garment or other article excluding anarticle of footwear). A sample including the component in a dry state(e.g., at approximately 25 degrees C. and approximately 20 percentrelative humidity) is cut from the article of apparel using a blade.This process is performed by separating the component of the article ofapparel from any associated component of the article of apparel. Forexample, if the component is present on a sleeve of a shirt, the sleevecomponent can be removed from the rest of the garment, and then thesample can be removed from the sleeve component.

If possible, any remaining or residual substances can be removed fromthe second surface of the component (e.g., the surface opposing theexternally-facing surface which comprises the elastomeric material) thatcan take up water and potentially skew the water uptake measurements ofthe elastomeric material. For example, any padding or additional layers,which are not externally facing during use, can be removed from thesecond side of the sample. For example, if appropriate, the secondsurface can be skinned, abraded, scraped, or otherwise cleaned to removeany upper adhesives, yarns, fibers, foams, and the like that couldpotentially take up water themselves.

The resulting sample may include the elastomeric material present on theside of the component configured to be externally-facing during use andany substrate or substrate affixed to the component, and, if one ispresent, maintains the interfacial bond between the component and theassociated substrate. As such, this test can simulate how the componentwill perform as part of an article of apparel. Additionally, this sampleis also useful in cases where the interfacial bond between the componentand the substrate or substrate is less defined, such as where theelastomeric material is highly diffused into the substrate (e.g., with aconcentration gradient).

The sample is taken at a location along the article of apparel thatprovides a substantially constant thickness for the material (within+/−10 percent of the average material thickness present in thecomponent), is taken from a portion of the component where soil wouldtypically accumulate during wear, and has a surface area of 4.0 squarecentimeters. In cases where the elastomeric material is not present onthe finished article in any segment having a 4.0 square centimetersurface area and/or where the thickness is not substantially constantfor a segment having a 4.0 square centimeter surface area, sample sizeswith smaller cross-sectional surface areas can be taken and thearea-specific measurements are adjusted accordingly.

(C)—Equipment Sampling Procedure

This procedure is used to obtain a sample of the elastomeric materialwhen the elastomeric material is present as a component in a finishedarticle of sporting equipment (e.g., when the component is affixed to asubstrate or substrate). A sample including the elastomeric material ina dry state (e.g., at approximately 25 degrees C. and approximately 20percent relative humidity) is cut from the article of sporting equipmentusing a blade. This process is performed by separating the componentfrom the finished article of sporting equipment. For example, if thecomponent is present on a portion of a golf bag, the portion of the golfbag comprising the elastomeric material can be removed from the rest ofthe golf bag.

If possible, any remaining substances can be removed from the secondsurface of the component (e.g., the surface opposing theexternally-facing surface which comprises the elastomeric material) thatcan take up water and potentially skew the water uptake measurements ofthe elastomeric material. For example, any padding or additional layers,which are not externally-facing during use, can be removed from thesecond side of the sample. For example, if appropriate, the secondsurface can be skinned, abraded, scraped, or otherwise cleaned to removeany adhesives, yarns, fibers, foams, and the like that could potentiallytake up water themselves.

The resulting sample includes the elastomeric material present on theexternally-facing side of the component and any substrate affixed to thecomponent, and, if one is present, maintains the interfacial bondbetween the material and the associated substrate or substrate. As such,this test can simulate how the component will perform as part of anarticle of sporting equipment. Additionally, this sample is also usefulin cases where the interfacial bond between the component and thesubstrate is less defined, such as where the elastomeric material ishighly diffused into the substrate or substrate (e.g., with aconcentration gradient).

The sample is taken at a location along the component of the article ofsporting equipment that provides a substantially constant thickness forthe material (within plus or minus 10 percent of the average thicknesspresent in the component). In addition, the sample is taken from aportion of the component where soil would typically accumulate duringwear, and has a surface area of 4.0 square centimeters. In cases, wherethe component is not present on the finished article in any segmenthaving a 4.0 square centimeter surface area and/or where the componentthickness is not substantially constant for a segment having a 4.0square centimeter surface area, sample sizes with smallercross-sectional surface areas can be taken and the area-specificmeasurements are adjusted accordingly.

Test Protocols

The following test procedures are described with reference to componentsof finished articles of footwear using the Materials Sampling Procedureor the Footwear Sampling Procedure as the Component Sampling Procedure.However, the same tests can be applied to samples taken with the ApparelSampling Procedure and/or the Equipment Sampling Procedure as theComponent Sampling Procedure.

(I)—Water Cycling Test Protocol

This test measures the mass stability of elastomeric materials bymeasuring the weight gain/loss that occurs upon the reversibleabsorption of water. Test samples are prepared by punching out 2.54 cm(1 inch) diameter disks from sheets of the elastomeric materials. Eachof the test samples is weighed prior to soaking in water with the massbeing recorded to the nearest milligram as the “initial” mass. The testsamples are then soaked in room-temperature water for a time interval of18-24 hours. To measure the total mass gain/loss of the elastomericmaterial, the test samples are removed from the water and patted drywith a laboratory wipe to remove free surface water. The test samplesare then allowed to dry in ambient laboratory conditions. The mass ofeach test sample is measured incrementally until a steady state isachieved over a 24 hour period. The final “dried” mass of each testsample is then measured and compared to the corresponding “initial”mass.

(II)—Water Uptake Capacity Test Protocol

This test measures the water uptake capacity of the elastomeric materialafter a predetermined soaking duration for a sample (e.g., taken withthe above-discussed Footwear Sampling Procedure). The sample isinitially dried at 60 degrees C. until there is no weight change forconsecutive measurement intervals of at least 30 minutes apart (e.g., a24-hour drying period at 60 degrees C. is typically a suitableduration). The total weight of the dried sample (Wt sample dry) is thenmeasured in grams. The dried sample is allowed to cool down to 25degrees C., and is fully immersed in a deionized water bath maintainedat 25 degrees C. After a given soaking duration, the sample is removedfrom the deionized water bath, blotted with a cloth to remove surfacewater, and the total weight of the soaked sample (Wt, sample wet) ismeasured in grams.

Any suitable soaking duration can be used, where a 24-hour soakingduration is believed to simulate saturation conditions for thehydrophilic resin or hydrogel of the present disclosure (i.e., thehydrophilic resin will be in its saturated state). Accordingly, as usedherein, the expression “having a water uptake capacity at 5 minutes”refers to a soaking duration of 5 minutes, the expression “having awater uptake capacity at 1 hour” refers to a soaking duration of 1 hour,the expression “having a water uptake capacity at 24 hours” refers to asoaking duration of 24 hours, and the like. If no time duration isindicated after a water uptake capacity value, the soaking durationcorresponds to a period of 24 hours. In an aspect, the elastomericmaterial can have a “time value” equilibrium water uptake capacity,where the time value corresponds to the duration of soaking. Forexample, a “30 second equilibrium water uptake capacity” corresponds toa soaking duration of 30 seconds, a 2 minute equilibrium water uptakecapacity corresponds to a soaking duration of 2 minutes, and so on atvarious time duration of soaking. A time duration of “0 seconds” refersto the dry-state and a time duration of 24 hours corresponds to thesaturated state of the elastomeric material.

As can be appreciated, the total weight of a sample taken pursuant tothe Footwear Sampling Procedure includes the weight of the material asdried or soaked (Wt. S. Dry or Wt. S. Wet) and the weight of thesubstrate (Wt. Sub.) needs to be subtracted from the samplemeasurements.

The weight of the substrate (Wt. Sub.) is calculated using the samplesurface area (e.g., 4.0 square centimeters), an average measuredthickness of the substrate in the sample, and the average density of thesubstrate material. Alternatively, if the density of the material forthe substrate is not known or obtainable, the weight of the substrate(Wt. Sub.) is determined by taking a second sample using the samesampling procedure as used for the primary sample, and having the samedimensions (surface area and film/substrate thicknesses) as the primarysample. The material of the second sample is then cut apart from thesubstrate of the second sample with a blade to provide an isolatedsubstrate. The isolated substrate is then dried at 60 degrees C. for 24hours, which can be performed at the same time as the primary sampledrying. The weight of the isolated substrate (Wt. Sub.) is then measuredin grams.

The resulting substrate weight (Wt. Sub.) is then subtracted from theweights of the dried and soaked primary sample (Wt. S. Dry or Wt. S.Wet) to provide the weights of the material as dried and soaked (Wt. C.Dry or Wt. C. Dry) as depicted by Equations 1 and 2.

Wt. C. Dry=Wt. S. Dry−Wt. Sub  (Eq. 1)

Wt. C. Wet=Wt. S. Wet−Wt. Sub.  (Eq. 2)

The weight of the dried component (Wt. C. Dry) is then subtracted fromthe weight of the soaked component (Wt. C. Wet) to provide the weight ofwater that was taken up by the component, which is then divided by theweight of the dried component (Wt. C. Dry) to provide the water uptakecapacity for the given soaking duration as a percentage, as depictedbelow by Equation 3.

$\begin{matrix}{{{Water}\mspace{14mu}{Uptake}\mspace{14mu}{Capacity}} = {\frac{{{Wt}.\mspace{14mu} C.\mspace{14mu}{Wet}} - {{Wt}.\mspace{14mu} C.\mspace{14mu}{Dry}}}{{Wt}.\mspace{14mu} C.\mspace{14mu}{Dry}}\left( {100\mspace{14mu}{percent}} \right)}} & \left( {{Eq}.\mspace{14mu} 3} \right)\end{matrix}$

For example, a water uptake capacity of 50 percent at 1 hour means thatthe soaked component weighed 1.5 times more than its dry-state weightafter soaking for 1 hour. Similarly, a water uptake capacity of 500percent at 24 hours means that the soaked component weighed 5 times morethan its dry-state weight after soaking for 24 hours.

(III)—Water Uptake Rate Test Protocol

This test measures the water uptake rate of the elastomeric material bymodeling weight gain as a function of soaking time for a sample with aone-dimensional diffusion model. The sample can be taken with any of theabove-discussed sampling procedures, including the Footwear SamplingProcedure. The sample is dried at 60 degrees C. until there is no weightchange for consecutive measurement intervals of at least 30 minutesapart (a 24-hour drying period at 60 degrees C. is typically a suitableduration). The total weight of the dried sample (Wt. S. Dry) is thenmeasured in grams. Additionally, the average thickness of the componentfor the dried sample is measured for use in calculating the water uptakerate, as explained below.

The dried sample is allowed to cool down to 25 degrees C., and is fullyimmersed in a deionized water bath maintained at 25 degrees C. Betweensoaking durations of 1, 2, 4, 9, 16, and 25 minutes, the sample isremoved from the deionized water bath, blotted with a cloth to removesurface water, and the total weight of the soaked sample (Wt. S. Wet) ismeasured at particular soaking-duration data points (e.g., 1, 2, 4, 9,16, or 25 minutes).

The exposed surface area of the soaked sample is also measured withcalipers for determining the specific weight gain, as explained below.The exposed surface area refers to the surface area that comes intocontact with the deionized water when fully immersed in the bath. Forsamples obtained using the Footwear Sampling Procedure, the samples onlyhave one major surface exposed. For convenience, the surface areas ofthe peripheral edges of the sample are ignored due to their relativelysmall dimensions.

The measured sample is fully immersed back in the deionized water bathbetween measurements. The 1, 2, 4, 9, 16, and 25 minute durations referto cumulative soaking durations while the sample is fully immersed inthe deionized water bath (i.e., after the first minute of soaking andfirst measurement, the sample is returned to the bath for one moreminute of soaking before measuring at the 2-minute mark).

As discussed above in the Water Uptake Capacity Test, the total weightof a sample taken pursuant to the Footwear Sampling Procedure includesthe weight of the material as dried or soaked (Wt. C. Wetor Wt. C. Dry)and the weight of the article or backing substrate (Wt. Sub.). In orderto determine a weight change of the material due to water uptake, theweight of the substrate (Wt. Sub.) needs to be subtracted from thesample weight measurements. This can be accomplished using the samesteps discussed above in the Water Uptake Capacity Test to provide theresulting material weights Wt. C. Wet and Wt. C. Dry for eachsoaking-duration measurement.

The specific weight gain (Wt. Gn.) water uptake for each soaked sampleis then calculated as the difference between the weight of the soakedsample (Wt. C. Wet) and the weight of the initial dried sample (W. C.Dry) where the resulting difference is then divided by the exposedsurface area of the soaked sample (A) as depicted in Equation 4.

$\begin{matrix}{\left( {{Wt}.\mspace{14mu} G.} \right) = \frac{\left( {{{Wt}.\mspace{14mu} C.\mspace{14mu}{Wet}} - {{Wt}.\mspace{14mu} C.\mspace{14mu}{Dry}}} \right)}{(A)}} & \left( {{Eq}.\mspace{14mu} 4} \right)\end{matrix}$

for a particular soaking-duration data point (e.g., 1, 2, 4, 9, 16, or25 minutes), as mentioned above.

The water uptake rate for the elastomeric material is then determined asthe slope of the specific weight gains Wt. G.) versus the square root oftime (in minutes) of the soaking duration, as determined by a leastsquares linear regression of the data points. For the elastomericmaterial of the present disclosure, the plot of the specific weightgains (Wt. G.) versus the square root of time (in minutes) of thesoaking duration provides an initial slope that is substantially linear(to provide the water uptake rate by the linear regression analysis).However, after a period of time depending on the thickness of thecomponent, the specific weight gains will slow down, indicating areduction in the water uptake rate, until the saturated state isreached. This is believed to be due to the water being sufficientlydiffused throughout the elastomeric material as the water uptakeapproaches saturation, and will vary depending on component thickness.

As such, for the component having an average thickness (as measuredabove) less than 0.3 millimeters, only the specific weight gain datapoints at 1, 2, 4, and 9 minutes are used in the linear regressionanalysis. In these cases, the data points at 16 and 25 minutes can beginto significantly diverge from the linear slope due to the water uptakeapproaching saturation, and are omitted from the linear regressionanalysis. In comparison, for the component having an average driedthickness (as measured above) of 0.3 millimeters or more, the specificweight gain data points at 1, 2, 4, 9, 16, and 25 minutes are used inthe linear regression analysis. The resulting slope defining the wateruptake rate for the sample has units of weight/(surface area-square rootof time), such as grams/(meter²−minutes^(1/2)) or g/m²√min.

Furthermore, some component surfaces can create surface phenomenon thatquickly attract and retain water molecules (e.g., via surface hydrogenbonding or capillary action) without actually drawing the watermolecules into the film or substrate. Thus, samples of these films orsubstrates can show rapid specific weight gains for the 1-minute sample,and possibly for the 2-minute sample. After that, however, furtherweight gain is negligible. As such, the linear regression analysis isonly applied if the specific weight gain in data points at 1, 2, and 4minutes continue to show an increase in water uptake. If not, the wateruptake rate under this test methodology is considered to be about zerog/m²√min.

(IV)—Swelling Capacity Test Protocol

This test measures the swelling capacity of the component in terms ofincreases in thickness and volume after a given soaking duration for asample (e.g., taken with the above-discussed Footwear SamplingProcedure). The sample is initially dried at 60 degrees C. until thereis no weight change for consecutive measurement intervals of at least 30minutes apart (a 24-hour drying period is typically a suitableduration). The dimensions of the dried sample are then measured (e.g.,thickness, length, and width for a rectangular sample; thickness anddiameter for a circular sample, etc.). The dried sample is then fullyimmersed in a deionized water bath maintained at 25 degrees C. After agiven soaking duration, the sample is removed from the deionized waterbath, blotted with a cloth to remove surface water, and the samedimensions for the soaked sample are re-measured.

Any suitable soaking duration can be used. Accordingly, as used herein,the expression “having a swelling thickness (or volume) increase at 5minutes of.” refers to a soaking duration of 5 minutes, the expression“having a swelling thickness (or volume) increase at 1 hour of” refersto a test duration of 1 hour, the expression “having a swellingthickness (or volume) increase at 24 hours of” refers to a test durationof 24 hours, and the like.

The swelling of the component is determined by (1) an increase in thethickness between the dried and soaked component, by (2) an increase inthe volume between the dried and soaked component, or (3) both. Theincrease in thickness between the dried and soaked components iscalculated by subtracting the measured thickness of the initial driedcomponent from the measured thickness of the soaked component.Similarly, the increase in volume between the dried and soakedcomponents is calculated by subtracting the measured volume of theinitial dried component from the measured volume of the soakedcomponent. The increases in the thickness and volume can also berepresented as percentage increases relative to the dry thickness orvolume, respectively.

(V)—Mud Pull-Off Test Protocol

This test measures, the force required to pull a test sample away from a5.1 cm (2 inches) diameter disk of mud (e.g., taken with theabove-discussed Footwear Sampling Procedure). Referring now to FIGS. 6Aand 6B, the test sample 200 and disk of mud 210 are placed between twoparallel aluminum plates 220(A, B). One of the aluminum plates 220A ismovable in a direction that his perpendicular to the alignment of theparallel plates. The other aluminum plate 220B is held stationary. Thetest sample is secured to the movable plate 220A.

When the two aluminum plates are separated 250 from each other the loadis set at zero Newton (N). The two plates are then compressed 260 withthe test material and the disk of mud located between them. The platesare compressed 260 (i.e., “loaded”) until the load applied reaches −445N (−100 lbs.). Once the load of −445 N is applied, the applied load isthen reversed 270 (i.e., “unloaded”). The pull-off force represents theload that is required to be applied in order to separate the testmaterial from the disk of mud. Thus, the pull-off force is the loadmeasured 280 that is above the zero threshold load. The pull-off forceis measured for each test material a total of 30 times with the final orrecorded pull-off force representing the average of the 30 measurements.

The following specific examples are given to illustrate the elastomericmaterial and the properties exhibited by and measured for suchcomposition. These specific examples should not be construed in a waythat limits the scope of the disclosure. Those skilled-in-the-art, inlight of the present disclosure, will appreciate that many changes canbe made in the specific embodiments which are disclosed herein and stillobtain alike or similar result without departing from or exceeding thespirit or scope of the disclosure. One skilled in the art will furtherunderstand that any properties reported herein represent properties thatare routinely measured and can be obtained by multiple differentmethods. The methods described herein represent one such method andother methods may be utilized without exceeding the scope of the presentdisclosure.

Example 1—Mud Pull-Off Test Results

The following test samples were prepared and tested according to the MudPull-Off Test Protocol and the Footwear Sampling Procedure as describedabove. One skilled in the art will understand that any of the SamplingProcedures can be utilized with similar results depending upon the typeof article in which the component is used. Each of the test samples(except Control #1) were prepared using a conventional rubberformulation of natural rubber, nitrile rubber, and polybutadiene as thecured rubber as part of the elastomeric material. In each of the testsamples (except Control #1) were prepared using a hydrogel as part ofthe elastomeric material as shown in Table 1. In Control #1, a standardTPU was used (Desmopan 8795A, Covestro AG, Leverkusen, Germany).

Referring now to FIG. 7 each of the samples (Control #1; Run #'s 1-4)were tested 30 times using the Mud Pull-Off Test protocol describedabove. Each of the test samples were prepared and soaked in water for aperiod of 24 hours prior to conducting the mud pull-off test. Thecontrol sample comprising only a standard TPU (Control 1) required a mudpull-off load or force ranging from about 1 Newton (N) to about 10 Nwith an overall average of about 6 Newton. In comparison, each of Run#'s 1-4, which included an elastomeric material according to the presentdisclosure exhibited a mud pull-off force that was less than about 0.3 Nwith an average mud pull-off force on the order of about 0.01 N for Run#1, about 0.05 N for Run #2, about 0.20 N for Run #3, and about 0.1 Nfor Run #4. This example demonstrates that the mud pull-off forceexhibited by a component comprising the elastomeric material of thepresent disclosure is lower than that expected for a component preparedsolely with a standard thermoplastic polyurethane.

TABLE 1 wt. percent (phr) Polymeric Hydrogel in the Elasomeric MaterialType of Polymeric Hydrogel Control 1 100 percent Desmopan 8795A TPU(Covestro AG, Leverkusen, Germany) Run 1 14 wt. percent (25 phr)Estane ® ALR-G2000 Hydrogel TPU Material, (Lubrizol Advanced MaterialsInc., Cleveland, OH) and cured rubber Run 2 57 wt. percent (200 phr)Estane ® ALR-G2000 Hydrogel TPU Material (Lubrizol Advanced MaterialsInc., Cleveland, OH) and cured rubber Run 3 24 wt. percent (50 phr)Estane ® ALR-L400 Hydrogel TPU Material (Lubrizol Advanced MaterialsInc., Cleveland, OH) and cured rubber Run 4 57 wt. percent (200 phr)Estane ® ALR-L400 Hydrogel TPU Material (Lubrizol Advanced MaterialsInc., Cleveland, OH) and cured rubber

Referring now to FIGS. 8A and 8B, a diagram of the applied force perunit area (i.e., Engineering Stress in MPa) plotted as a function ofdisplacement can also be obtained by conducting this type of test. Thisplot demonstrates that the mixing of a hydrophilic resin with a curedrubber enhances the compliance of the resulting elastomeric material orlayer. The greatest stress values are measured for the sample (Control#2) in which no hydrophilic resin (0 phr) is present, but rather onlythe cured rubber, i.e., a mixture of natural rubber, nitrile rubber, andpolybutadiene. The compliance of the elastomeric material increases asthe amount of the hydrophilic resin or hydrogel that is mixed with thecured rubber increases (i.e., from 0 phr to 43.75 phr as shown in Runnumbers 5 to 8). In addition, a larger effect is observed when theelastomeric material in the component is wet, e.g., soaked for a periodof 24 hours (see FIG. 8B) as compared to being dry (see FIG. 8A). Oneskilled in the art will understand that water exposure has little effecton only the cured rubber as shown by comparing the 0 phr curves (Control#2) in FIGS. 8A and 8B.

Example 2—Water Uptake Rate & Capacity Results

Test samples were prepared by mixing various amounts (50 phr, 100 phr,150 phr, & 200 phr) of a hydrophilic resin (e.g., either ALR-L400 orALR-G2000, Lubrizol Advanced Materials Inc.) into a conventional curedrubber (i.e., a mixture of natural rubber, nitrile rubber, andpolybutadiene). The test samples were then subjected to both the WaterUptake Rate Test protocol and the Overall Water Uptake Capacity Testprotocol. Referring now to FIGS. 9A and 9B. As the amount of thehydrophilic resin or hydrogel in the crosslinked elastomeric materialincreases, the water uptake rate also increases. The water uptake rateover the range of 50 phr to 200 phr of a hydrophilic TPU (ALR-L400)added to an elastomeric rubber (FIG. 9A) increased from about 25g/m²√min to about 72 g/m²√min. Similarly, the water uptake rate over therange 25 phr to 100 phr of a hydrophilic TPU (ALR-G2000) added to thesame cured rubber (FIG. 9B) increased from about 14 g/m²√min to about 57g/m²√min. Although there is a slight difference in the water uptake ratedepending upon the composition of the hydrophilic resin, the same trendis observed as the loading of the hydrophilic resin is increased.Similar results are also observed when the hydrophilic resin is apolyether block amide (i.e., contains hydrophilic polyether groups andrigid polyamide groups), such as PEBAX 1074, commercially available fromArkema Specialty Polyamides, France.

Referring now to FIG. 10, the same trend is also observed as the loadingof the hydrophilic resin is increased when using different compositionsof a cured rubber. In FIG. 9, the water uptake rate is plotted as afunction of hydrophilic resin loading for elastomeric materialscontaining different cured rubber mixtures. The difference between thecured rubber mixtures resides in both the quantity of differentconventional rubbers as well as the use of natural rubber and regrindmaterials (in Rubber A) versus a synthetic rubber and virgin materials(in Rubber B).

Referring once again to FIGS. 9A and 9B, the overall water capacity ofthe elastomeric materials increased as the loading of the hydrophilicresin (e.g., ALR-L400 or ALR-G2000) increased. The overall watercapacity after a 24-hour soak time for the elastomeric material in Runs9-12 increased from 59 percent to 194 percent, while the overall watercapacity for the elastomeric materials in Runs 13-16 increased from 35percent to 170 percent.

Referring now to FIGS. 11A and 11B, photomicrographs of mud present onthe surface of a component soaked for a period of 24 hours are shown. InFIG. 11A, the mud is more compact (i.e., substantial accumulation) sincethe component does not comprise any polymeric hydrogel (0 phr), butrather only a conventional cured rubber (Control 2). In comparison, themud shown in FIG. 11B is found to be more dispersed (i.e., less hasaccumulated) on the surface of a component that comprises a total of 50phr of a polymeric hydrogel (ALR-G2000, Lubrizol) mixed with the curedrubber in an elastomeric material according to the present disclosure.

Example 3—Swelling Test Results

A test sample comprising Control #2 in which no hydrophilic resin (0phr) is present, but rather only the cured rubber, i.e., a mixture ofnatural rubber, nitrile rubber, and polybutadiene. Test samples werealso prepared mixing the cured rubber of Control #2 with a hydrophilicTPU resin (ALR-G2000, Lubrizol) at 25 phr (Run 17), 50 phr (Run 18), and75 phr (Run 18). All of the test samples (Control #2, Runs 17-19) wererectangular in shape and measured 15.25 cm (6 inches) by 10.15 cm (4inches). Each of the test samples were subjected to the SwellingCapacity Test for a period of 24 hours.

The results of this test are visually depicted in FIG. 12. The Control#2 was observed not to swell, while each the test samples (Runs 17-19)were found to swell, such that the degree of swelling increased as theamount of the polymeric hydrogel present in the elastomeric materialincreased. In other words, the degree of swelling followed theprogression of Run 17<Run 18<Run 19.

Example 4—Water Cycling Test Results

The following test samples were prepared and tested according to theWater Cycling Test Protocol and the Material Sampling Procedure asdescribed above. A test sample was prepared by mixing 100 phr, of ahydrophilic thermoplastic urethane (TPU) resin (ALR-G2000, LubrizolAdvanced Materials Inc.) into a conventional cured rubber (i.e., amixture of natural rubber, nitrile rubber, and polybutadiene) accordingto the teachings of the present disclosure. Similar test samples wereprepared with the hydrophilic resin being substituted with a polyacrylicacid (either AP75 or AP93, Evonik Corp., Alabama). The weightmeasurements for each test sample taken initially, after completion ofthe Water Cycling Test protocol are provided in Table 2 below.

TABLE 2 Total Polymeric After After Soak - After change in hydrogelOriginal Soak Weight Gain Dry Weight type (100 phr) Mass (g) (g) (percent) (g) ( percent) Run 20 Polymeric 1099 2095 47.50 1167 5.8hydrogel percent (ALR-G2000, Lubrizol Adv. Mat. Inc.) Run 21 PolymericPolymeric hydrogel 758 992 hydrogel 629 −17.06 (AP75, Evonik flaked offCorporation) sample Run 22 Polymeric Polymeric hydrogel 757 929 hydrogel590 −22.1 (AP93, Evonik flaked off Corporation) sample

This example demonstrates that the use of a thermoplastic polyurethane(TPU) as defined herein as a hydrogel added to an uncured rubber andthen cured results in no weight loss upon exposure to water. Rather asshown in Run 20, the elastomeric material formed according to theteachings of the present disclosure resulted in a weight gain of 5.8weight percent after the Water Cycling Testing. In comparison, the testsamples that incorporated polyacrylic acid (PAA) as shown in Runs 21 and22 were observed to flake during water exposure and result in in overallweight loss in the Water Cycle Test ranging from about −17 weightpercent to about −22 weight percent.

Referring now to FIGS. 13A and 13B, the surface of the elastomericmaterial 300 in test sample Run 20 was observed to be visibly similar tothe elastomeric material 300C in the original (i.e., initial dry) state.However, upon exposure to water for only 30 seconds differences betweenthe test samples (Runs 20 & 22) become self-evident. More specifically,in Run 22 (see FIG. 13A), the polymeric hydrogel is observed to swell asshown by the dark regions 305 visibly observable in the photomicrograph.In Run 22, the polymeric hydrogel (dark regions) 305 are shown in thephotomicrograph to be separated from the cured rubber 310. Incomparison, in Run 20, the elastomeric material 300 formed according tothe teachings of the present disclosure exhibits uniform surfaceswelling with no separation of the thermoplastic polyurethane (TPU)polymeric hydrogel and the cured rubber being observable.

CLAUSES

Clause 1. A composition comprising: a rubber; and a polymeric hydrogel;wherein, in the composition, the polymeric hydrogel is distributedthroughout the rubber.Clause 2. The composition of clause 1, wherein the rubber is an uncuredrubber and wherein, in the composition, the polymeric hydrogel isdistributed throughout the uncured rubber.Clause 3. The composition of any preceding clause, wherein the rubber isa cured rubber, wherein the composition is an elastomeric material,wherein, in the elastomeric material, the polymeric hydrogel isdistributed throughout the cured rubber and at least a portion of thepolymeric hydrogel in the elastomeric material is entrapped by the curedrubber, wherein optionally the polymeric hydrogel is physicallyentrapped by the cured rubber, or is chemically bonded to the curedrubber, or is both physically entrapped by the cured rubber andchemically bonded to the cured rubber.Clause 4. The composition of clause 3, wherein the composition of thepolymeric hydrogel and the cured rubber has a water uptake of at least40 percent by weight, based on a total weight of the composition, or atleast 60 percent by weight, or at least 80 percent by weight, or atleast 100 percent by weight.Clause 5. The composition of any preceding clause, wherein the polymerichydrogel comprises a polyurethane hydrogel, and optionally wherein thepolyurethane hydrogel is a reaction polymer of a diisocyanate with apolyol.Clause 6. The structure of any preceding clause, wherein thepolyurethane hydrogel comprises a thermoplastic polyurethane (TPU) whichincludes a plurality of alkoxy segments and a plurality of diisocyanatesegments, wherein the plurality of diisocyanate segments are linked toeach other by chain extending segments; optionally wherein the TPU is areaction polymer of a diisocyanate with a polyol; or optionally whereinthe diisocyanate segments comprise an aliphatic diisocyanate segment, anaromatic diisocyanate segment, or both.Clause 7. The composition of any preceding clause, wherein thediisocyanate segments comprise aliphatic diisocyanate segments;optionally wherein the aliphatic diisocyanate segments includehexamethylene diisocyanate (HDI) segments; optionally wherein a majorityof the diisocyanate segments are HDI segments; and optionally whereinthe aliphatic diisocyanate segments include isophorone diisocyanate(IPDI) segments.Clause 8. The composition of any preceding clause, wherein thediisocyanate segments includes aromatic diisocyanate segments;optionally wherein the aromatic diisocyanate segments includediphenylmethane diisocyanate (MDI) segments; and optionally wherein thearomatic diisocyanate segments include toluene diisocyanate (TDI)segments.Clause 9. The composition of any preceding clause, wherein the alkoxysegments include ester segments and ether segments, or optionallywherein the alkoxy segments include ester segments, or optionallywherein the alkoxy segments include ether segments.Clause 10. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a polyamide hydrogel, optionally whereinthe polyamide hydrogel is a reaction polymer of a condensation ofdiamino compounds with dicarboxylic acids.Clause 11. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a polyurea hydrogel, optionally wherein thepolyurea hydrogel is a reaction polymer of a diisocyanate with adiamine.Clause 12. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a polyester hydrogel, optionally whereinthe polyester hydrogel is a reaction polymer of a dicarboxylic acid witha diol.Clause 13. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a polycarbonate hydrogel, optionallywherein the polycarbonate hydrogel is a reaction polymer of a diol withphosgene or a carbonate diester.Clause 14. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a polyetheramide hydrogel, optionallywherein the polyetheramide hydrogel is a reaction polymer ofdicarboxylic acid and polyether diamine.Clause 15. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a hydrogel formed of addition polymers ofethylenically unsaturated monomers.Clause 16. The composition of any preceding clause, wherein thepolymeric hydrogel comprises a hydrogel formed of a copolymer, whereinthe copolymer is a combination of two or more types of polymers withineach polymer chain, optionally wherein the copolymer is selected fromthe group consisting of: a polyurethane/polyurea copolymer, apolyurethane/polyester copolymer, and a polyester/polycarbonatecopolymer.Clause 17. The composition of any preceding clause, wherein the hydrogelcomprises a plurality of copolymer chains, each copolymer chainindependently having a combination of hard segments (HS) and softsegments, wherein each of the soft segments (SS) independently includesa plurality of hydroxyl groups, one or more poly(ethylene oxide) (PEO)segments, or both; optionally wherein each of the soft segments (SS) ofthe polymeric hydrogel independently has a greater level ofhydrophilicity than each of the hard segments (HS); and optionallywherein an average ratio of a number of soft segments to a number hardsegments (SS:HS) present in the copolymer chains of the polymerichydrogel range from about 6:1 to about 100:1.Clause 18. The composition of any preceding clause, wherein thepolymeric hydrogel has a water uptake capacity in the range of about 50weight percent to about 2000 weight percent, as measured using the WaterUptake Capacity Test with the Material Sampling Procedure; optionallywherein the polymeric hydrogel has a water uptake capacity in the rangeof about 100 weight percent to about 1500 weight percent, or wherein thepolymeric hydrogel has a water uptake capacity in the range of about 300weight percent to about 1200 weight percent.Clause 19. The composition of any preceding clause, wherein thepolymeric hydrogel has a water uptake rate of 10 g/m²√min to 120g/m²√min as measured using the Water Uptake Rate Test with the MaterialSampling Procedure.Clause 20. The composition of any preceding clause, wherein thecomposition includes from about 0.5 parts per hundred resin to about 85parts per hundred resin of the polymeric hydrogel based on an overallweight of the composition, wherein the composition includes from about 5parts per hundred to about 80 parts per hundred of the polymerichydrogel based on an overall weight of the composition, wherein thecomposition includes from about 10 parts per hundred to about 75 partsper hundred of the polymeric hydrogel based on an overall weight of thecomposition, or wherein the composition includes from about 20 parts perhundred to about 70 parts per hundred of the polymeric hydrogel based onan overall weight of the composition.Clause 21. The composition of any preceding clause, wherein thecomposition includes a colorant, and the colorant is selected from adye, pigment, or combination thereof.Clause 22. The composition of any preceding clause, wherein the uncuredrubber comprises an uncured natural rubber, or an uncured syntheticrubber, or both.Clause 23. The composition of any preceding clause, wherein the uncuredrubber is an uncured butadiene rubber, an uncured styrene-butadiene(SBR) rubber, an uncured butyl rubber, an uncured isoprene rubber, anuncured nitrile rubber, an uncured urethane rubber, or any combinationthereof.Clause 24. The composition of any preceding clause, wherein thecomposition further comprises a crosslinking agent for crosslinking theuncured rubber, optionally wherein the crosslinking agent is a thermallyinitiated crosslinking agent; and optionally wherein the thermallyinitiated crosslinking agent is a sulfur-based crosslinking agent or aperoxide-based crosslinking agent.Clause 25. The composition of any preceding clause, wherein the uncuredrubber is an actinic radiation curable rubber, and the crosslinkingagent is an initiator for crosslinking the radiation curable rubber uponexposure to actinic radiation.Clause 26. The composition of any preceding clause, wherein theelastomeric material is a crosslinked reaction product of a mixturecomprising the polymeric hydrogel and the rubber.Clause 27. The composition of any preceding clause, wherein at least aportion of the polymeric hydrogel is entrapped in the elastomericmaterial, optionally wherein the polymeric hydrogel is covalently bondedto the cured rubber.Clause 28. The composition of any preceding clause, whereinsubstantially all the polymeric hydrogel in the elastomeric material isphysically entrapped by the cured rubber.Clause 29. The composition of any preceding clause, wherein the curedrubber is a cured butadiene rubber, a cured styrene-butadiene (SBR)rubber, a cured butyl rubber, a cured isoprene rubber, a cured nitrilerubber, a cured urethane rubber, or a combination thereof.Clause 30. The composition of any preceding clause, wherein theelastomeric material has an equilibrium water uptake capacity of atleast 20 weight percent, or at least 40 weight percent, or at least 60weight percent, or at least 80 weight percent.Clause 31. The composition of any preceding clause, wherein theelastomeric material has an equilibrium water uptake capacity of atleast 100 weight percent.Clause 32. The composition of any preceding clause, wherein theelastomeric material has a water cycling weight loss from about 0 weightpercent to about 15 weight percent as measured using the Water CyclingTest with the Material Sampling Procedure.Clause 33. An article comprising: an elastomeric material including acured rubber and a polymeric hydrogel; wherein, in the elastomericmaterial, the polymeric hydrogel is distributed throughout the curedrubber, and at least a portion of the polymeric hydrogel present in theelastomeric material is entrapped by the cured rubber.Clause 34. The article of clause 33, wherein the elastomeric materialfurther comprises a first colorant homogeneously distributed throughoutthe elastomeric material.Clause 35. The article of any preceding clause, wherein the elastomericmaterial further comprises a first colorant is heterogeneouslydistributed throughout the elastomeric material.Clause 36. The article of any preceding clause, wherein the elastomericmaterial further comprises one or more colorants.Clause 37. The article of any preceding clause, wherein the elastomericmaterial is one as described in one of clauses of the preceding clauses.Clause 38. The article of any preceding clause, wherein the article hasa water cycling weight loss of less than 10 weight percent.Clause 39. The article of any preceding clause, wherein the elastomericmaterial has a dry-state thickness in the range of about 0.2 mm to about2.0 mm.Clause 40. The article of any preceding clause, wherein the elastomericmaterial has a saturated-state thickness that is at least 100 percentgreater than the dry-state thickness of the elastomeric material orwherein the saturated-state thickness of the elastomeric material is atleast 200 percent greater than the dry-state thickness of theelastomeric material.Clause 41. The article of any preceding clause, wherein the elastomericmaterial is attached to a textile, and optionally the textile is a knittextile, a woven textile, a non-woven textile, a braided textile acrocheted textile, or any combination thereof.Clause 42. The article of any preceding clause, wherein elastomericmaterial comprises a plurality of fibers, one or more yarns, one or moretextiles, or any combination thereof.Clause 43. The article of any preceding clause, wherein the elastomericmaterial is attached to, a plurality of fibers, one or more yarns, oneor more textiles, or any combination thereof, wherein the plurality offibers, the one or more yarns, the one or more textiles, or thecombination thereof, comprise synthetic fibers.Clause 44. The article of any preceding clause, wherein the syntheticfibers or yarns comprise, consist of, or consist essentially of athermoplastic composition, and optionally the thermoplastic compositioncomprises, consists of, or consists essentially of a thermoplasticpolyurethane (TPU), a thermoplastic polyamide, a thermoplasticpolyester, a thermoplastic polyolefin, or a mixture thereof.Clause 45. The article of any preceding clause, wherein the plurality offibers, the one or more yarns, the one or more textiles, or anycombination thereof, is a filler or as a reinforcing element, andoptionally wherein the plurality of fibers are dispersed in elastomericmaterial, or wherein the elastomeric material infiltrates the yarnand/or the textile and consolidates the fibers of the yarn and/or thefibers or yarn of the textile.Clause 46. The article of any preceding clause, wherein the article isan article of footwear, a component of footwear, an article of apparel,a component of apparel, an article of sporting equipment, or a componentof sporting equipment.Clause 47. The article of any preceding clause, wherein the article isan article of footwear, and optionally wherein the article is a solecomponent for an article of footwear.Clause 48. The article of any preceding clause, further comprising afirst layer comprising the elastomeric material and a second layercomprising a cured rubber, wherein the first layer and the second layeris attached to one another by crosslinks between the cured rubber of thefirst layer and the cured rubber of the second layer.Clause 49. The article of any preceding clause, wherein the secondcomprises one or more of the traction elements, wherein the tractionelements are on a side of the article of footwear configured to beground facing.Clause 50. The article of any preceding clause, wherein the tractionelements are selected from the group consisting of: a cleat, a stud, aspike, and a lug.Clause 51. The article of any preceding clause, wherein the tractionelements are integrally formed with an outsole of the article offootwear.Clause 52. The article of any preceding clause, wherein the tractionelements are removable traction elements.Clause 53. The article of any preceding clause, wherein the elastomericmaterial is not disposed on tip of the traction element configured to beground contacting.Clause 54. The article of any preceding clause, wherein the elastomericmaterial is disposed in an area separating the traction elements andoptionally on one or more sides of the traction elements.Clause 55. An article of footwear comprising: an upper; and an outsolecomprising a first region having a first elastomeric material; whereinthe first region defines a portion of an externally facing side of theoutsole, and wherein the first elastomeric material includes a mixtureof a first cured rubber and a first polymeric hydrogel at a firstconcentration; wherein, in the first elastomeric material, the firstpolymeric hydrogel is distributed throughout the first cured rubber andat least a portion of the first polymeric hydrogel present in the firstelastomeric material is entrapped by the first cured rubber, wherein thefirst elastomeric material is capable of taking up water.Clause 56. The article of clause 55, wherein the outsole comprises asecond region having a second elastomeric material, wherein the firstregion and the second region are adjacent one another, wherein thesecond region defines a portion of the externally facing side of theoutsole, and wherein the second elastomeric material includes a mixtureof a second cured rubber and a second polymeric hydrogel at a secondconcentration, wherein, in the second elastomeric material, the secondpolymeric hydrogel is distributed throughout the second cured rubber andat least a portion of the second polymeric hydrogel present in thesecond elastomeric material is entrapped by the second cured rubber.Clause 57. The article of any preceding clause, wherein the firsthydrogel and the second hydrogel are the same.Clause 58. The article of any preceding clause, wherein the firsthydrogel and second hydrogel are different.Clause 59. The article of any preceding clause, wherein the firsthydrogel and second hydrogel concentrations are the same.Clause 60. The article of any preceding clause, wherein the firsthydrogel and second hydrogel concentrations are different.Clause 61. The article of any preceding clause, wherein the firstelastomeric material comprises a first colorant at a firstconcentration.Clause 62. The article of any preceding clause, wherein the secondelastomeric material comprises a second colorant at a secondconcentration.Clause 63. The article of any preceding clause, wherein the first andsecond colorants are the same.Clause 64. The article of any preceding clause, wherein the first andsecond colorant concentrations are the same.Clause 65. The article of any preceding clause, wherein the first andsecond colorant concentrations are different.Clause 66. The article of any preceding clause, wherein the externallyfacing side of the article formed by the elastomeric material has a mudpull-off force that is less than about 12 Newton as determined by theMud Pull-Off Test using the Component Sampling Procedure.Clause 67. The article of any preceding clause, wherein the elastomericmaterial is any preceding clause.Clause 68. The article of any preceding clause, wherein the article offootwear comprises one or more of the traction elements, wherein thetraction elements are on a side of the article of footwear configured tobe ground facing; optionally wherein the traction elements are selectedfrom the group consisting of: a cleat, a stud, a spike, and a lug,optionally wherein the one or more traction elements include tractionelements integrally formed with an outsole of the article of footwear ortraction elements which are removable traction elements, or both;optionally wherein the elastomeric material is not disposed on tip ofthe traction element configured to be ground contacting; and optionallywherein the elastomeric material is disposed in an area separating thetraction elements and optionally on one or more sides of the tractionelements.Clause 69. The article of any preceding clause, further comprising afirst layer comprising the elastomeric material and a second layercomprising a rubber, wherein the first layer and the second layer isattached to one another by crosslinks between the cured rubber of thefirst layer and the cured rubber of the second layer.Clause 70. A method of making an article, comprising: attaching a firstcomponent and a second component including the elastomeric material ofany preceding clause to one another, thereby forming the article.Clause 71. The method of any preceding clause, wherein the article is anarticle of footwear, an article of apparel, or an article of sportingequipment or wherein the first component is an upper component for anarticle of footwear, or wherein the second component is a sole componentfor an article of footwear.Clause 72. The method of any preceding clause, wherein the step ofattaching is attaching the sole component such that the externallyfacing layer of the elastomeric material forms at least a portion of aside of the sole component which is configured to be externally facing.Clause 73. The method of any preceding clause, further comprisingdisposing the elastomeric material in an area separating the tractionelements and optionally on one or more sides of the traction elements.Clause 74. The method of any preceding claim, further comprising a firstcomponent comprising a first material and a second component comprisinga second material, wherein attaching the first component and the secondcomponent comprises curing the first material and the second material incontact with each other and forming chemical bonds between a firstmaterial and the second material, optionally wherein, prior to thecuring, the first material is a first uncured composition or a firstpartially cured elastomeric material and the second material is a seconduncured composition or a second partially cured elastomeric material, oris a second uncured or partially cured rubber substantially free of apolymeric hydrogel, and forming chemical bonds between the firstmaterial and the second material includes fully curing the rubber of thefirst and second materials and forming crosslinking bonds between therubber of the first and second materials.Clause 75. An article comprising: a product of the method of anypreceding clause.Clause 76. The article of clause 75, wherein the first component is asubstrate that comprises a polymeric foam, a molded solid polymericmaterial, a textile, or a combination thereof, and the second componentis attached to the first component.Clause 77. The article of any preceding clause, wherein the firstcomponent is a substrate that includes a thermoset polymeric material, athermoplastic polymeric material, or both.Clause 78. The article of any preceding clause, wherein thethermoplastic polymeric material includes a thermoplastic polyurethane,a thermoplastic polyester, a thermoplastic polyamide, a thermoplasticpolyolefin, or any combination thereof.Clause 79. The article of any preceding clause, wherein the firstcomponent includes a textile, wherein the textile is selected from aknit textile, a woven textile, a non-woven textile, a braided textile,or a combination thereof.Clause 80. The article of any preceding clause, wherein the textileincludes fibers or yarns formed from a thermoplastic polymeric materialthat includes a thermoplastic polyurethane, a thermoplastic polyester, athermoplastic polyamide, a thermoplastic polyolefin, or any combinationthereof.Clause 81. An article of any preceding clause, wherein the article is anoutsole including a first elastomeric material; wherein the firstelastomeric material forms a first portion of an externally-facing sideof the outsole; wherein the first elastomeric material includes amixture of a first cured rubber and a first polymeric hydrogel at afirst concentration, in which the first polymeric hydrogel isdistributed throughout and entrapped by a first polymeric networkincluding the first cured rubber, and the first elastomeric material hasa water uptake capacity of at least 40 percent by weight based on atotal weight of the first elastomeric material present in the firstportion.Clause 82. A method of preparing a composition, the method comprising:providing an uncured rubber; providing a polymeric hydrogel; and mixingthe uncured rubber and the polymeric hydrogel together to distribute thepolymeric hydrogel throughout the uncured rubber, forming thecomposition.Clause 83. The method of clause 138, wherein the composition is thecomposition of any preceding clause.Clause 84. The method of any preceding clause, wherein the step ofmixing included mixing the uncured rubber and the polymeric hydrogeltogether until they are substantially blended.Clause 85. The method of any preceding clause, further comprisingshaping the mixed composition.Clause 86. The method of any preceding clause, wherein shaping the mixedcomposition includes forming the mixed composition into a sheet ormolding the mixed composition into a shape.Clause 87. The method of any preceding clause, further comprisingexposing the composition to actinic radiation in an amount and for aduration to at least partially cure the mixed composition to form anelastomeric material.Clause 88. A composition prepared according to the method of precedingclause.Clause 89. An elastomeric material prepared according to the method ofclause 88.Clause 90. A method of forming an elastomeric material, the methodcomprising: providing a composition including a mixture of an uncuredrubber and a polymeric hydrogel, wherein, in the composition, thepolymeric hydrogel is distributed throughout the uncured rubber; andcuring the composition to form the elastomeric material, wherein thepolymeric hydrogel is distributed throughout the cured rubber and atleast a portion of the polymeric hydrogel present in the elastomericmaterial is entrapped by the cured rubber.Clause 91. An elastomeric material prepared according to any precedingclause.Clause 92. A method of forming an article, the method comprising:providing a composition including a mixture of an uncured rubber and apolymeric hydrogel; wherein, in the composition, the polymeric hydrogelis distributed throughout the uncured rubber; shaping the composition toform a shaped composition; and curing the shaped composition to cure theuncured rubber of the composition and form the article, the articlecomprising an elastomeric material in which the polymeric hydrogel isdistributed throughout the cured rubber and at least a portion of thepolymeric hydrogel in the elastomeric material is entrapped by curedrubber.Clause 93. The method of any preceding clause, wherein the shapingincludes extruding, calendaring, molding, thermoforming, or anycombination thereof, the composition to form the shaped composition.Clause 94. The method of any preceding clause, wherein the curingincludes exposing the composition to actinic radiation in an amount andfor a duration sufficient to at least partially cure the composition.Clause 95. The method of any preceding clause, wherein the curingincludes exposing the composition to actinic radiation in an amount andfor a duration sufficient to fully cure the composition.Clause 96. The method of any preceding clause, wherein the methodfurther comprises shaping the article after the curing.Clause 97. The method of any preceding clause, wherein the shaping thearticle includes cutting, molding, thermoforming, or any combinationthereof, the elastomeric material of the article.Clause 98. The method of any preceding clause, wherein the shapedcomposition is disposed on a first layer comprising an uncured rubber orpartially cured rubber, wherein curing the shaped composition furthercomprises curing the uncured rubber or partially cured rubber of thecomposition and the uncured rubber of the first layer and formingcrosslinking bonds between the cured rubber in the shaped compositionand cured rubber in the first layer, forming crosslinking bonds betweenthe cured rubber in the first layer and polymeric hydrogel, or acombination thereof.Clause 99. A method of forming an outsole, the method comprising:shaping a first composition to form a first portion of anexternally-facing side an outsole, wherein the first compositionincludes a mixture of a first uncured or partially cured rubber and afirst polymeric hydrogel at a first concentration, wherein the firstpolymeric hydrogel is distributed throughout the first uncured orpartially cured rubber; and curing the first portion to form a firstelastomeric material, thereby curing the first uncured or partiallycured rubber into a first fully cured rubber, and forming a firstpolymeric network including the first fully cured rubber in the firstelastomeric material, wherein the first polymeric hydrogel isdistributed throughout and entrapped by the first polymeric network.Clause 100. The method of any preceding clause, wherein the article isan outsole, and the method comprises: the shaping the second compositioncomprises placing the second composition in a second region of a mold,wherein the second region of the mold is configured to form tractionelements; the shaping the first composition and contacting the at leastan edge of the first portion with the at least an edge of the secondportion comprises placing the first composition in a first region of themold, wherein the first region of the mold is configured to form asubstrate for the traction elements, and placing the first compositionin the first region of the mold comprises contacting a second side ofthe second portion with a first side of the first portion; the curingcomprises curing fully curing both the first portion and the secondportion in the mold and bonding the first side of the first portion tothe second side of the second portion; and following the curing,removing the bonded first portion and second from the mold.Clause 101. The method of any preceding clause, wherein the curingincludes exposing the first composition to actinic radiation in anamount and for a duration sufficient to fully cure the first uncured orpartially cured rubber of the first composition.Clause 102. The method of any preceding clause, further comprising:shaping a second composition to form a second portion of theexternally-facing side the outsole, wherein the second compositionincludes a second uncured or partially cured rubber; and curing theshaped second composition, forming a second material including a secondfully cured rubber.Clause 103. The method of any preceding clause, further comprising:contacting at least an edge of the first portion with at least an edgeof the second portion; and wherein the curing comprises curing the firstportion or the second portion or both while the at least an edge of thefirst portion and the at least an edge of the second portion are incontact, and comprises forming crosslinking bonds between the firstuncured or partially cured rubber and the second uncured or partiallycured rubber during the curing, thereby bonding the first portion to thesecond portion.Clause 104. The method of any preceding clause, wherein the shapingcomprises forming one or more traction elements from the secondcomposition.Clause 105. An article prepared according to the method of any ofclauses.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeis explicitly recited. To illustrate, a concentration range of “about0.1 percent to about 5 percent” should be interpreted to include notonly the explicitly recited concentration of about 0.1 wt percent toabout 5 wt percent, but also include individual concentrations (e.g., 1percent, 2 percent, 3 percent, and 4 percent) and the sub-ranges (e.g.,0.5 percent, 1.1 percent, 2.2 percent, 3.3 percent, and 4.4 percent)within the indicated range. The term “about” can include traditionalrounding according to significant figures of the numerical value. Inaddition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about‘y’”.

Many variations and modifications may be made to the above-describedaspects, embodiments and examples. All such modifications and variationsare intended to be included herein within the scope of this disclosureand protected by the following claims.

What is claimed:
 1. An outsole comprising: a first elastomeric material;wherein the first elastomeric material forms a first portion of anexternally-facing side of the outsole; wherein the first elastomericmaterial includes a mixture of a first cured rubber and a firstpolymeric hydrogel at a first concentration, in which the firstpolymeric hydrogel is distributed throughout and entrapped by a firstpolymeric network including the first cured rubber, and the firstelastomeric material has a water uptake capacity of at least 40 percentby weight based on a total weight of the first elastomeric materialpresent in the first portion; wherein the outsole comprises a secondmaterial, wherein the second material forms a second portion of theexternally-facing side of the outsole, wherein at least a first edge ofthe first portion and at least a second edge of the second portioncontact one another, wherein the second material includes a second curedrubber that is substantially free of one or more polymeric hydrogels;and wherein the second portion and the first portion are attached to oneanother by crosslinking bonds, and an interface between the firstportion and the second portion is substantially free of adhesive.
 2. Theoutsole of claim 1, wherein first polymeric hydrogel is physicallyentrapped by the first polymeric network, or is chemically bonded to thefirst polymeric network, or both.
 3. The outsole of claim 1, wherein thefirst polymeric hydrogel is selected from the group consisting of: apolyurethane hydrogel, a polyamide hydrogel, a polyurea hydrogel, apolyester hydrogel, a polycarbonate hydrogel, and a polyetheramidehydrogel.
 4. The outsole of claim 1, wherein the first polymerichydrogel comprises a polyurethane hydrogel.
 5. The outsole of claim 1,wherein the first elastomeric material includes a colorant, and thecolorant is selected from a dye, pigment, or combination thereof.
 6. Theoutsole of claim 1, wherein first elastomeric material includes fromabout 30 weight percent to about 70 weight percent of the firstpolymeric hydrogel based on a total weight of the first elastomericmaterial present in the first portion.
 7. The outsole of claim 1,wherein the second material forms one or more traction elements on theexternally-facing side of the outsole.
 8. The outsole of claim 7,wherein the first portion is an area separating the two or more tractionelements.
 9. The outsole of claim 7, wherein the traction elements areselected from the group consisting of: a cleat, a stud, a spike, and alug.
 10. The outsole of claim 7, wherein the traction elements areintegrally formed with an outsole of the article of footwear.
 11. Theoutsole of claim 7, wherein the traction elements are removable tractionelements.
 12. The outsole of claim 7, wherein the elastomeric materialis not disposed on tip of the traction element configured to be groundcontacting.
 13. The outsole of claim 7, wherein the second cured rubberis a cured butadiene rubber, a cured styrene-butadiene (SBR) rubber, acured butyl rubber, a cured isoprene rubber, a cured nitrile rubber, acured urethane rubber, or a combination thereof.
 14. The outsole ofclaim 7, wherein the first elastomeric material is attached to atextile.
 15. The outsole of claim 14, wherein the textile is a knittextile, a woven textile, a non-woven textile, a braided textile acrocheted textile, or any combination thereof.
 16. The outsole of claim1, wherein first elastomeric material comprises a plurality of fibers,one or more yarns, one or more textiles, or any combination thereof. 17.The outsole of claim 1, wherein the first elastomeric material isattached to, a plurality of fibers, one or more yarns, one or moretextiles, or any combination thereof.
 18. The outsole of claim 1,wherein the first elastomeric material is attached to a midsole.
 19. Theoutsole of claim 1, wherein the first elastomeric material is attachedto a substrate that comprises a polymeric foam, a molded solid polymericmaterial, a textile, or a combination thereof.